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WO2025189061A1 - Réduction de résidus dans des dispersions d'alcane perfluoroalcoxy (pfa) - Google Patents

Réduction de résidus dans des dispersions d'alcane perfluoroalcoxy (pfa)

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Publication number
WO2025189061A1
WO2025189061A1 PCT/US2025/018847 US2025018847W WO2025189061A1 WO 2025189061 A1 WO2025189061 A1 WO 2025189061A1 US 2025018847 W US2025018847 W US 2025018847W WO 2025189061 A1 WO2025189061 A1 WO 2025189061A1
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WO
WIPO (PCT)
Prior art keywords
dispersion
pfa
linear
less
ether
Prior art date
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Pending
Application number
PCT/US2025/018847
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WO2025189061A8 (fr
Inventor
Kimberly Dawn Farnsworth
Rachael PICKENS
Ethan Edward BLYTHE
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.)
Chemours Co FC LLC
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Chemours Co FC LLC
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Application filed by Chemours Co FC LLC filed Critical Chemours Co FC LLC
Publication of WO2025189061A1 publication Critical patent/WO2025189061A1/fr
Publication of WO2025189061A8 publication Critical patent/WO2025189061A8/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/16—Purification

Definitions

  • the present disclosure is related to the field of fluoropolymers. More specifically, the present disclosure is related to perfluoroalkoxy alkane (PFA) dispersions and composition having reduced residue levels and processes of forming the same.
  • PFA perfluoroalkoxy alkane
  • Fluoropolymers are applied to a wide number of substrates in order to confer release, chemical and heat resistance, corrosion protection, cleanability, low flammability, and weatherability.
  • One method of applying fluoropolymers to substrates is by dispersion coating, i.e. , applying the dispersion in dispersion form to the substrate with the subsequent application of heat for drying and coalescence.
  • Dispersion coating processes typically employ fluoropolymer dispersions in a more concentrated form than the as-polymerized dispersion.
  • dispersions are often concentrated, such as, for example, by the method taught in U.S. Patent No. 3,037,953, which includes the addition of a nonionic surfactant to the as-polymerized dispersion, heating to above the cloud point, and removing the clear upper supernate that forms above the concentrated dispersion.
  • basic compounds such as, for example, ammonium hydroxide or sodium hydroxide, are added to increases the pH of the dispersion sufficiently such that bacteria do not grow.
  • the concentrated dispersions used for dispersion coating thus may contain a significant quantity of nonionic surfactant, e.g., 6-8 wt % percent based on the weight of fluoropolymer solids in the dispersion.
  • Dispersion coating processes using concentrated dispersions include the steps of applying concentrated dispersion to a substrate by common techniques such as spraying, roller or curtain coating, drying the substrate to remove volatile components (primarily water and nonionic surfactant), and baking the substrate. When baking temperatures are high enough, the primary dispersion particles fuse and become a coherent mass. Baking at high temperatures to fuse particles of non-melt-processible fluoropolymer is often referred to as sintering.
  • fluorosurfactants are used as non-telogenic dispersing agents in the manufacture of aqueous fluoropolymer dispersions and thus, unless removed, fluorosurfactants are normally present in aqueous fluoropolymer dispersions. Due to environmental concerns, it is frequently desirable to reduce the fluorosurfactant content and content of other fluorinated residues of fluoropolymer dispersions.
  • fluorinated residuals of manufactured fluoropolymers include certain impurities from the manufacturing process, including perfluoroalkyl carboxylic acids (PFCAs).
  • PFCAs perfluoroalkyl carboxylic acids
  • a conventional process of aqueous emulsion polymerization to form a dispersion of a copolymer of tetrafluoroethylene and perfluoroalkylvinyl ether (PFA) dispersion produces significant levels of PFCAs in the dispersion.
  • a PFA is a copolymer of tetrafluoroethylene (TFE) and perfluoroalkylvinyl ether (PAVE).
  • Short chain PAVEs include perfluoromethylvinyl ether (PMVE), perfluoroethylvinyl ether (PEVE), and perfluoropropylvinyl ether (PPVE).
  • PFCA levels particularly the levels of the linear (i.e., unbranched) perfluoroalkyl carboxylic acids C8-C14, are being subject to increasing regulatory control.
  • the linear C8 PFCA is n-perfluorooctanoic acid (CsFizCOOH; PFOA; C8).
  • the linear C9-C14 perfluoroalkyl carboxylic acids include n-perfluorononanoic acid (C9F19COOH; PFNA; C9), n-perfluorodecanoic acid (C10F21COOH; PFDA; C10), n-perfluoroundecanoic acid (C11F23COOH; PFUDA; C11), n-perfluorododecanoic acid (C12F25COOH; PFDoA; C12), n-perfluorotridecanoic acid (C13F27COOH; PFTrDA; C13), and n-perfluorotetradecanoic acid (C14F29COOH; PFTeDA; C14).
  • n-perfluorononanoic acid C9F19COOH; PFNA; C9
  • n-perfluorodecanoic acid C10F21COOH; PFDA; C10
  • a process produces an aqueous PFA fluoropolymer dispersion with low linear C9-C14 perfluoroalkyl carboxylic acid content by first polymerizing at least one fluoromonomer in an aqueous medium in the presence of a fluorosurfactant and a nucleant to produce the aqueous PFA fluoropolymer dispersion having an initial linear C9-C14 perfluoroalkyl carboxylic acid content and fluoropolymer particles having a raw dispersion particle size of less than 180 nm.
  • the process also includes modifying the fluorosurfactant dispersion by adding a nonionic surfactant to the fluorosurfactant dispersion, contacting the modified fluoropolymer dispersion with an ion exchange resin to remove fluorinated surfactant and to reduce the linear C9-C14 perfluoroalkyl carboxylic acid content to a predetermined level, and separating the anion exchange resin from the dispersion after the linear C9-C14 perfluoroalkyl carboxylic acid content has been reduced.
  • the process further includes concentrating the PFA dispersion to a predetermined final solids percent.
  • a perfluoroalkoxy alkane (PFA) dispersion comprises particles of perfluoroalkoxy alkane dispersed in an aqueous liquid.
  • the particles have a raw dispersion particle size of less than 180 nm.
  • the PFA dispersion has a solids content of at least 20 wt% and a total concentration of linear C9-C14 perfluoroalkyl carboxylic acids of about 500 parts-per-bil lion or less.
  • the perfluoroalkane is a copolymer of tetrafluoroethylene and a comonomer selected from the group consisting of perfluoromethylvinyl ether, perfluoroethylvinyl ether, perfluoropropylvinyl ether, and a combination thereof.
  • the comonomer is perfluoromethylvinyl ether.
  • the comonomer is perfluoroethylvinyl ether.
  • the comonomer is perfluoropropylvinyl ether.
  • the raw dispersion particle size is less than 170 nm.
  • the total concentration of linear C9-C14 perfluoroalkyl carboxylic acids is about 200 parts-per-billion or less.
  • the total concentration of linear C9-C14 perfluoroalkyl carboxylic acids is about 100 parts-per-billion or less.
  • the solids content is at least 40 wt%.
  • a process comprises contacting a perfluoroalkoxy alkane (PFA) dispersion having a first cumulative concentration of linear C9-C14 perfluoroalkyl carboxylic acids to an ion exchange resin to remove at least 95% of the linear C9-C14 perfluoroalkyl carboxylic acids from the PFA dispersion.
  • PFA perfluoroalkoxy alkane
  • the ion exchange resin comprises counterions selected from the group consisting of hydroxyl, proton, and chloride and has a resin functionality selected from the group consisting of Type I, Type II, tributylammonium, and quaternary ammonium.
  • the ion exchange resin is a strong base anion resin.
  • the ion exchange resin is polystyrenic gel Type II ion exchange resin.
  • the process further comprises selecting a concentration of a nucleant to form the PFA dispersion by dispersion polymerization to have a raw dispersion particle size of less than 180 nm.
  • the raw dispersion particle size is less than 170 nm.
  • the process further comprises forming the PFA dispersion having a raw dispersion particle size of less than 180 nm with the selected concentration of the nucleant.
  • the nucleant is a perfluoropolyether carboxylic acid.
  • the PFA dispersion comprises particles of perfluoroalkoxy alkane dispersed in an aqueous liquid.
  • the perfluoroalkoxy alkane is a copolymer of tetrafluoroethylene and a comonomer selected from the group consisting of perfluoromethylvinyl ether, perfluoroethylvinyl ether, perfluoropropylvinyl ether, and a combination thereof.
  • the comonomer is perfluoromethylvinyl ether.
  • the comonomer is perfluoroethylvinyl ether.
  • the comonomer is perfluoropropylvinyl ether.
  • the PFA dispersion has a solids content of at least 20 wt% and a total concentration of linear C9-C14 perfluoroalkyl carboxylic acids of about 500 parts-per-bil lion or less.
  • the process further comprises separating the PFA dispersion from the ion exchange resin.
  • the process further comprises concentrating the PFA dispersion to a final solids content of at least 40 percent, by weight.
  • the total concentration of linear COCI 4 perfluoroalkyl carboxylic acids is about 200 parts-per-billion or less.
  • the total concentration of linear COCI 4 perfluoroalkyl carboxylic acids is about 100 parts-per-billion or less.
  • dispersion coating processes typically employ fluoropolymer dispersions in a more concentrated form than the as-polymerized dispersion, i.e., the concentrated dispersions have a final fluoropolymer solids content of about 35 to about 70 wt %.
  • These concentrated dispersions contain surfactants and a significant quantity of nonionic surfactant in the range of 2-11 wt %, typically 6-8 wt % based on the weight of fluoropolymer in the dispersion.
  • These concentrated dispersions also contain a significant quantity of fluorinated residues, including linear C9-C14 perfluoroalkyl carboxylic acids.
  • PFA compositions and PFA dispersions having reduced levels of linear C9-C14 perfluoroalkyl carboxylic acids and methods of forming such compositions and dispersions.
  • a perfluoroalkoxy alkane (PFA) dispersion includes particles of perfluoroalkoxy alkane dispersed in an aqueous liquid.
  • the particles have a raw dispersion particle size (RDPS) of less than 180 nm.
  • RDPS raw dispersion particle size
  • the PFA dispersion has a solids content of at least 20 wt% and a total concentration of linear C9-C14 perfluoroalkyl carboxylic acids of about 500 parts-per-bil lion or less (ppb).
  • the perfluoroalkylvinyl ether (PAVE) of the PFA is perfluoromethylvinyl ether (PMVE), perfluoroethylvinyl ether (PEVE), perfluoropropylvinyl ether (PPVE), and a combination thereof.
  • the comonomer includes PMVE.
  • the comonomer includes PEVE.
  • the comonomer includes PPVE.
  • Appropriate amounts of PAVE include, but are not limited to, up to about 12 wt%, alternatively about 0.1 to about 12 wt%, alternatively about 1 to about 10 wt%, alternatively about 2 to about 8 wt%, alternatively about 3 to about 5 wt%, or any value, range, or sub-range therebetween, based on the total weight of the PFA polymer.
  • An appropriate raw dispersion particle size may include, but is not limited to, less than 190 nm, alternatively 189 nm to about 150 nm, alternatively less than 180 nm, alternatively 179 nm to about 150 nm, alternatively 175 nm to about 150 nm, alternatively about 170 nm to about 150 nm, alternatively about 170 nm to about 160 nm, alternatively about 160 nm to about 150 nm, or any value, range, or subrange therebetween.
  • An appropriate total concentration of linear C9-C14 perfluoroalkyl carboxylic acids may include, but is not limited to, about 500 ppb or less, about 200 ppb or less, alternatively about 150 ppb or less, alternatively about 100 ppb or less, alternatively about 75 ppb or less, alternatively about 50 ppb or less, or any value, range, or subrange therebetween.
  • An appropriate solids content may include, but is not limited to, at least 20 wt%, alternatively at least 30 wt%, alternatively about 20 wt% to about 70 wt%, alternatively about 30 wt% to about 60 wt%, alternatively about 20 wt% to about 60 wt%, alternatively about 40 wt% to about 60 wt%, or any value, range, or sub-range therebetween.
  • Aqueous fluoropolymer dispersions are useful as coating or impregnating compositions and to make cast films.
  • a process produces an aqueous PFA fluoropolymer dispersion with a low linear C9-C14 perfluoroalkyl carboxylic acid content by first polymerizing at least one fluoromonomer in an aqueous medium in the presence of at least one fluorosurfactant and a nucleant in a predetermined amount to produce the aqueous PFA fluoropolymer dispersion having an initial linear C9-C14 perfluoroalkyl carboxylic acid content and fluoropolymer particles having a raw dispersion particle size (RDPS) of less than 180 nm.
  • RDPS raw dispersion particle size
  • the polymerization occurs in an aqueous solution including a nucleant and one or more surfactants.
  • concentration of the nucleant is selected to form the PFA dispersion by dispersion polymerization to have a predetermined raw dispersion particle size.
  • the dispersion polymerization occurs by a process as described in U.S. Patent No. 8,519,072 or in U.S. Patent No. 9,732,212, which are incorporated by reference herein.
  • the RDPS is achieved, selected, or controlled by a process as described in U.S. Patent No. 9,732,212.
  • the dispersion polymerization includes copolymerization of tetrafluoroethylene (TFE) and perfluoroalkylvinyl ether (PAVE) in an aqueous dispersion including a nucleant and a fluorosurfactant.
  • TFE tetrafluoroethylene
  • PAVE perfluoroalkylvinyl ether
  • Appropriate nucleants may include, but are not limited to, water-soluble hydrocarbon-containing surfactants, nonionic hydrocarbon-containing surfactants, cationic hydrocarbon-containing surfactants, or perfluoropolyethers.
  • Appropriate nonionic surfactant nucleants may include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, their derivatives, and the like. More specifically, appropriate polyoxyethylene alkyl ethers may include, but are not limited to, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, and the like.
  • appropriate polyoxyethylene alkyl phenyl ethers may include, but are not limited to, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether and the like.
  • appropriate polyoxyethylene alkyl esters may include, but are not limited to, polyethylene glycol monolaurylate, polyethylene glycol monooleate, polyethylene glycol monostearate and the like.
  • appropriate sorbitan alkyl esters may include, but are not limited to, polyoxyethylene sorbitan monolaurylate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and the like.
  • appropriate polyoxyethylene sorbitan alkyl esters may include, but are not limited to, polyoxyethylene sorbitan monolaurylate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and the like.
  • appropriate glycerol esters may include, but are not limited to, glycerol monomyristate, glycerol monostearate, glycerol monooleate, and the like.
  • appropriate derivatives may include, but are not limited to, polyoxyethylene alkyl amine, polyoxyethylene alkyl phenyl-formaldehyde condensate, polyoxyethylene alkyl ether phosphate, and the like.
  • Particularly preferable nonionic surfactant nucleants include polyoxyethylene alkyl ethers and polyoxyethylene alkyl esters. Particularly preferable nonionic surfactant nucleants have a hydrophilic-lipophilic balance (HLB) value of 10 to 18. Particularly preferable nonionic surfactant nucleants include polyoxyethylene lauryl ether (5 to 20 ethylene oxide units), polyethylene glycol monostearate 10 to 55 ethylene oxide units), and polyethylene glycol monooleate (6 to 10 ethylene oxide units).
  • HLB hydrophilic-lipophilic balance
  • Appropriate perfluoropolyether nucleants may include, but are not limited to, perfluoropolyether carboxylic acids, such as, for example, KrytoxTM 157FSH (The Chemours Company FC, LLC, Wilmington, DE) nucleant, which has the chemical structure C 3 H7-O-(CF(CF3)-CF2-O)n-CF(CF 3 )-COOH.
  • perfluoropolyether carboxylic acids such as, for example, KrytoxTM 157FSH (The Chemours Company FC, LLC, Wilmington, DE) nucleant, which has the chemical structure C 3 H7-O-(CF(CF3)-CF2-O)n-CF(CF 3 )-COOH.
  • the surfactants include a polymeric fluorosurfactant or a non-polymeric fluorosurfactant.
  • Appropriate fluorosurfactants may include, but are not limited to, a non- telogenic, anionic dispersing agent, soluble in water and including an anionic hydrophilic group and a hydrophobic portion.
  • the hydrophobic portion is an aliphatic fluoroalkyl group containing at least four carbon atoms, all except at most one of which, and that one the closest to the solubilizing group, bearing at least two fluorine atoms, the terminal carbon atom bearing in addition an atom consisting of hydrogen or fluorine.
  • fluorosurfactants are used as a polymerization aid for dispersing and because they do not chain transfer, they do not cause formation of polymer with undesirable short chain length.
  • the fluorosurfactant is a perfluorinated carboxylic acid having 6-10 carbon atoms and is typically used in salt form.
  • suitable fluorosurfactants include ammonium perfluorocarboxylates, such as, for example, ammonium perfluorocaprylate or ammonium perfluorooctanoate.
  • the fluorosurfactant is 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propionic acid.
  • the fluorosurfactants are usually present in the amount of 0.02 to 1 wt % with respect to the amount of polymer formed.
  • the polymerization conditions are selected to provide fluoropolymer particles having a predetermined raw dispersion particle size (RDPS).
  • RDPS raw dispersion particle size
  • the predetermined raw dispersion particle size is less than 180 nm.
  • an increased concentration of nucleant provides the predetermined RDPS.
  • a decreased reaction time provides the predetermined RDPS.
  • a process includes modifying the aqueous PFA fluoropolymer dispersion by adding nonionic surfactant to the aqueous PFA fluoropolymer dispersion after producing the aqueous PFA fluoropolymer dispersion.
  • Nonionic surfactants may include, but are not limited to, TergitolTM TMN-10 or TergitolTM TMN-6 surfactant (The Dow Chemical Company, Midland, Ml).
  • Other additives may be added during the modifying, including, but not limited to, ethylenediaminetetraacetic acid (EDTA); a base, such as, for example, ammonium hydroxide, to adjust the pH; a viscosity reducer and/or ion replacer, such as, for example, ammonium sulfate; ammonium fluoride; and/or water.
  • EDTA ethylenediaminetetraacetic acid
  • base such as, for example, ammonium hydroxide
  • a viscosity reducer and/or ion replacer such as, for example, ammonium sulfate; ammonium fluoride; and/or water.
  • a process includes contacting the modified aqueous PFA fluoropolymer dispersion containing linear C9-C14 perfluoroalkyl carboxylic acid with an ion exchange resin to reduce linear C9-C14 perfluoroalkyl carboxylic acid content to a predetermined level or by a predetermined percentage.
  • Appropriate ion exchange resin counterions may include, but are not limited to, hydroxyl, proton, or chloride counterions.
  • the ion exchange resin is a strong base anion resin.
  • the ion exchange resin is a polystyrenic gel Type II resin.
  • Appropriate ion exchange resin functionalities may include, but are not limited to, Type I, Type II, tributylammonium, or quaternary ammonium.
  • Appropriate ion exchange resin backbones may include, but are not limited to, divinylbenzene-crosslinked polystyrene or divinylbenzene-crosslinked polyacrylate.
  • Appropriate ion exchange resin porosities may include, but are not limited, porous, microporous, hyperporous, or gel.
  • Appropriate commercial ion exchange resins may include, but are not limited to, PurofineTM PFA300, PurofineTM PFA300OH, PurofineTM PFA694, PurofineTM PFA694E, PuroliteTM A501 P, PuroliteTM A850, or PuroliteTM A860 ion exchange resins (Purolite Company, King of Prussia, PA); CalRes 2301 or CalRes2304 (Calgon Carbon Corporation, Pittsburgh, PA); AmberLiteTM PSR2 Plus or AmberLiteTM IRA458 ion exchange resins (E. I.
  • DIAIONTM SAF12A DIAIONTM SAF11AL, DIAIONTM HPA25M, DIAIONTM HPA512L, or DIAIONTM PA312 ion exchange resins (Mitsubishi Chemical Corporation, Tokyo, Japan); or LewatitTM TP106, LewatitTM TP108, or LewatitTM MonoPlus TP109 ion exchange resins (Lanxess Deutschland GmbH, Cologne, Germany).
  • any of a variety of techniques that bring the dispersion in contact with the anion exchange resin and then separate the dispersion from the anion exchange resin can be used for carrying out the ion exchange process.
  • the process can be carried out by addition of ion exchange resin bead to the dispersion in a stirred tank, in which a slurry of the dispersion and resin is formed, followed by separation of the dispersion from the anion exchange resin beads by filtration.
  • Another suitable method is to pass the dispersion through a fixed bed of anion exchange resin instead of using a stirred tank. Flow can be upward or downward through the bed and no separate separation step is needed beyond the flowing since the resin remains in the fixed bed.
  • a process includes concentrating an aqueous PFA fluoropolymer dispersion having a reduced linear C9-C14 perfluoroalkyl carboxylic acid content to a predetermined solids percent.
  • the concentrating is by a method taught in U.S. Patent No. 3,037,953, which is incorporated by reference herein.
  • the concentrating includes adding a nonionic surfactant to the as polymerized dispersion, heating to above the cloud point, and removing the clear upper supernatant layer forming above the concentrated dispersion.
  • the heating is to about 60 to about 70°C for about 2 to about 4 hours.
  • Both particle size analyzers operate on the similar principle of a dynamic light scattering (DLS) technique and are expected to provide similar results.
  • DLS dynamic light scattering
  • the Zetasizer particle size analyzer uses the Stokes- Einstein relationship to determine the RDPS from the DLS data, whereas the Nanotrac particle size analyzer uses Mie calculation theory to determine the RDPS from the DLS data.
  • melt flow rate was measured according to ASTM D-1238 using a 5-kg weight on the molten polymer at a melt temperature which is standard for the specific copolymer.
  • MRM Multiple Reaction Monitoring
  • the RDPS of CE1 was measured to be about 192 nm.
  • the percent solids of CE1 was determined to be about 27.1 wt%, and the melt flow rate (MFR) was about 2 g/10 min.
  • MFR melt flow rate
  • the individual concentrations of linear C4-C14 PFCAs in the dispersion were measured. Table 1 shows the measured individual concentrations in parts-per-billion (ppb) of C8-C14 PFCAs and the summed total amount of measured linear C9-C14 PFCAs in CE1 prior to ion exchange (OX).
  • the RDPS of CE2 was measured to be about 190-200 nm.
  • the percent solids of CE2 was determined to be about 33.8 wt%, and the MFR was about 2 g/10 min.
  • the individual concentrations of linear C4- C14 PFCAs in the dispersion were measured.
  • Table 2 shows the measured individual concentrations ppb of C8-C14 PFCAs and the summed total amount of measured linear C9-C14 PFCAs in CE2 prior to ion exchange (OX).
  • the measured differences between CE1 and CE2 show the potential variability between different batches.
  • Inventive Examples having a smaller RDPS than that of CE1 and CE2 were synthesized.
  • the vinyl ether for Inventive Example 1 (IE1) and Inventive Example 4 was perfluoropropylvinyl ether (PPVE).
  • the vinyl ether for Inventive Example 2 (IE2), Inventive Example 3 (IE3), and Inventive Example 5 (IE5) was perfluoroethylvinyl ether (PEVE).
  • the Inventive Examples were synthesized by the same dispersion polymerization process as for the Comparative Examples, except that a higher initial concentration of the nucleant was provided in the reaction mixture to give a lower raw dispersion particle size (RDPS) than for the Comparative Examples.
  • RDPS raw dispersion particle size
  • Inventive Example 1 had an RDPS of about 169 nm. The percent solids was determined to be about 19.8 wt%. The MFR was about 2 g/10 min.
  • Inventive Example 2 had an RDPS of about 164 nm. The percent solids was determined to be about 27.2 wt%. The MFR was about 7 g/10 min.
  • Inventive Example 3 had an RDPS of about 151 nm. The percent solids was determined to be about 21.4 wt%. The MFR was about 16 g/10 min.
  • Inventive Example 4 had an RDPS of about 160-170 nm. The percent solids was determined to be about 34.2 wt%. The MFR was about 2 g/10 min.
  • Inventive Example 5 had an RDPS of about 150-170 nm. The percent solids was determined to be about 35.1 wt%. The MFR was about 7 g/10 min.
  • Comparative Example 1 and Inventive Examples 1, 2, and 3 were applied to a PurofineTM PFA300OH ion exchange resin on a column at a first scale.
  • the individual concentrations of linear C4-C14 PFCAs in the dispersion were measured after a first pass through the column (1X) and again after a second pass through the column (2X).
  • Table 1 shows the measured individual concentrations in ppb of C8- C14 PFCAs and the summed total amount of measured linear C9-C14 PFCAs.
  • Comparative Example 2 and Inventive Examples 4 and 5 were applied to a PurofineTM PFA300OH ion exchange resin on a column at a second scale larger than the first scale.
  • the individual concentrations of linear C4-C14 PFCAs in the dispersion were measured after a first pass through the column (1X) and again after a second pass through the same column (2X).
  • Table 2 shows the measured individual concentrations in ppb of C8-C14 PFCAs and the summed total amount of measured linear C9-C14 PFCAs.
  • the concentrations for IE5 prior to ion exchange and after one ion exchange are the averages of three measurements.
  • the concentrations for IE5 after two ion exchange are the averages of two measurements.
  • Comparative Example 2 and Inventive Examples 4 and 5 were concentrated (C) to about 60 wt% solids and the individual concentrations of PFCAs were measured. The results are shown in Table 3 along with the 2X concentrations for comparison. The concentrations for IE5 are an average of three measurements.
  • Table 3 shows that the concentrations of the PFCAs roughly doubled upon roughly doubling the percent solids, indicating that the PFCAs were likely associated with the PFA particles rather than the liquid in the dispersions.
  • the Comparative Examples included more surfactant during polymerization than the Inventive Examples. To rule out a role of surfactant concentration, surfactant was added to an Inventive Example after polymerization but prior to ion exchange with a negligible effect on the ion exchange effectiveness.

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Abstract

L'invention concerne un procédé qui comprend la mise en contact d'une dispersion d'alcane perfluoroalcoxy (PFA) ayant une première concentration cumulative d'acides perfluoroalkylcarboxyliques linéaires en C9-C14 à une résine échangeuse d'ions pour éliminer au moins 95 % des acides perfluoroalkylcarboxyliques linéaires en C9-C14 de la dispersion PFA. Une dispersion de PFA contient des particules d'alcane perfluoroalcoxy dispersées dans un liquide aqueux. Les particules présentent une taille de particule de dispersion brute inférieure à 180 nm. La dispersion de PFA a une teneur en solides d'au moins 20 % en poids et une concentration totale d'acides perfluoroalkylcarboxyliques linéaires en C9-C14 inférieure ou égale à environ 500 parties par milliard.
PCT/US2025/018847 2024-03-08 2025-03-07 Réduction de résidus dans des dispersions d'alcane perfluoroalcoxy (pfa) Pending WO2025189061A1 (fr)

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Citations (7)

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US3037953A (en) 1961-04-26 1962-06-05 Du Pont Concentration of aqueous colloidal dispersions of polytetrafluoroethylene
US6833403B1 (en) * 1998-12-11 2004-12-21 3M Innovative Properties Company Aqueous dispersions of fluoropolymers
US8519072B2 (en) 2006-11-09 2013-08-27 E I Du Pont De Nemours And Company Aqueous polymerization of fluorinated monomer using polymerization agent comprising fluoropolyether acid or salt and short chain fluorosurfactant
US9732212B2 (en) 2008-05-09 2017-08-15 The Chemours Company Fc, Llc Aqueous polymerization of fluorinated monomer using a mixture of fluoropolyether acids or salts
WO2024024891A1 (fr) * 2022-07-27 2024-02-01 ダイキン工業株式会社 Dispersion aqueuse de polymère fluoré ainsi que procédé de fabrication de celle-ci, et composition de matériau de revêtement
WO2024024917A1 (fr) * 2022-07-27 2024-02-01 ダイキン工業株式会社 Dispersion aqueuse de polymère fluoré ainsi que procédé de fabrication de celle-ci, et composition de matériau de revêtement

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