US20070025902A1 - Recovery of fluorinated carboxylic acid from adsorbent particles - Google Patents

Recovery of fluorinated carboxylic acid from adsorbent particles Download PDF

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US20070025902A1
US20070025902A1 US11/420,413 US42041306A US2007025902A1 US 20070025902 A1 US20070025902 A1 US 20070025902A1 US 42041306 A US42041306 A US 42041306A US 2007025902 A1 US2007025902 A1 US 2007025902A1
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cooh
chf
fluorinated
carboxylic acid
process according
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US11/420,413
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Klaus Hintzer
Michael Jurgens
Harald Kaspar
Herbert Koenigsmann
Kai Lochhaas
Andreas Maurer
Werner Schwertfeger
Tilman Zipplies
George Moore
Jay Schulz
Richard Flynn
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority claimed from GBGB0514387.0A external-priority patent/GB0514387D0/en
Priority claimed from GBGB0514398.7A external-priority patent/GB0514398D0/en
Priority claimed from GBGB0523853.0A external-priority patent/GB0523853D0/en
Priority claimed from GBGB0525978.3A external-priority patent/GB0525978D0/en
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Assigned to 3M INNOVATIVE PROPERTIES COMPANY reassignment 3M INNOVATIVE PROPERTIES COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FLYNN, RICHARD M., MOORE, GEORGE G.I., SCHULZ, JAY F., LOCHHAAS, KAI HELMUT, MAURER, ANDREAS R., SCHWERTFEGER, WERNER, HINTZER, KLAUS, JURGENS, MICHAEL, KASPAR, HARALD, KOENIGSMANN, HERBERT, ZIPPLIES, TILMAN
Publication of US20070025902A1 publication Critical patent/US20070025902A1/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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
    • C08L27/02Compositions 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
    • C08L27/12Compositions 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02Polyalkylene oxides
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/30Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]

Definitions

  • the fluorosurfactant used in the polymerization processes is typically removed from the dispersions and waste streams generated in the manufacturing of the fluoropolymer, including waste waters and exhaust gas.
  • An effective and frequently used method involves adsorbing the fluorosurfactant to adsorbent particles such as activated carbon and anion exchange resins. Such processes have been described in EP 1514848, EP 1093441, EP 1084097 and WO 2005/082785.
  • the fluorosurfactant is typically recovered there from using an eluting liquid as disclosed in for example EP 0014431, EP1069078, U.S. Pat. No. 6,642,415, EP 1323677 and U.S. Pat. No. 3,882,153.
  • fluorinated carboxylic acid is hereinafter used to indicate the free acid as well as salts thereof.
  • the fluorinated carboxylic acid used in the process of the invention corresponds to formula (I) above.
  • the fluorinated carboxylic acid will be a low molecular weight compound, for example a compound having a molecular weight for the anion part of the compound of not more than 1000 g/mol, typically not more than 600 g/mol and in particular embodiments, the anion of the fluorinated carboxylic acid may have a molecular weight of not more than 500 g/mol.
  • L represents a linking group.
  • the linking group can be a linear partially or fully fluorinated alkylene.
  • Fully fluorinated alkylene groups include alkylene groups that consist of only carbon and fluorine atoms whereas partially fluorinated alkylene groups may additionally contain hydrogen.
  • a partially fluorinated alkylene group should not contain more than 2 hydrogen atoms so as to be highly fluorinated and be non-telogenic or at least have minimal telogenic effects.
  • Examples of fully fluorinated alkylene groups include linear perfluorinated alkylenes that have from 1 to 6 carbon atoms, for example linear perfluorinated alkylene groups of 1, 2, 3, 4 or 5 carbon atoms.
  • the linking group L is an aliphatic hydrocarbon group.
  • aliphatic hydrocarbon groups include linear, branched or cyclic aliphatic groups.
  • Particular examples of aliphatic groups include linear or branched alkylene groups of 1 to 4 carbon atoms such as for example methylene or ethylene.
  • R f may correspond to the following formula: R 7 f —(O) t —CFH—CF 2 — (III)
  • R f may correspond to the following formula: R f 1 —(OCF 2 ) a — (IV)
  • R f 8 is a linear partially fluorinated aliphatic group or a linear fully fluorinated aliphatic group having 1, 2, 3 or 4 carbon atoms.
  • R f 8 is a partially fluorinated aliphatic group
  • the number of carbon atoms preferably is between 1 and 6 and the number of hydrogen atoms in the partially fluorinated aliphatic groups is preferably 1 or 2.
  • R f a represents a linear partially or fully fluorinated aliphatic group optionally interrupted with one or more oxygen atoms, t is 0 or 1 and n is 0 or 1, X i+ represents a cation having a valence i and i is 1, 2 or 3, with the proviso that when t is 0, the R f a contains at least one ether oxygen atom.
  • R a f and t are as defined above.
  • Compounds according to formula (VIa) are well known in the art and include fluorinated olefins such as perfluorinated alkyl vinyl compounds, vinyl ethers in particular perfluorovinyl ethers and allyl ethers, in particular perfluorinated allyl ethers.
  • Fluorinated carboxylic acids according to formula (VI) wherein n is 0 can be prepared by reacting a fluorinated olefin of formula (VIa) with a base. The reaction is generally carried out in aqueous media.
  • An organic solvent may be added to improve the solubility of the fluorinated olefin. Examples of organic solvents include glyme, tetrahydrofuran (THF) and acetonitrile. Additionally or alternatively a phase transfer catalyst may be used.
  • a base use can be made of for example ammonia, alkali and earth alkali hydroxides.
  • the reaction is generally carried out between 0 and 200° C., for example between 20-150° C. and at a pressure between about 1 bar up to about 20 bar.
  • the obtained salts can be distilled via the free acid or by first converting the acid into an ester derivative and then distilling the ester derivative followed by hydolysis of the ester to obtain the purified acid or salt thereof.
  • a free radical reaction of the fluorinated olefin of formula (VIa) with methanol may be carried out followed by an oxidation of the resulting reaction product.
  • the free radical reaction is typically carried out using a free radical initiator as is typically used in a free radical polymerization reaction.
  • suitable free radical initiators include persulfates such as for example ammonium persulfate.
  • the resulting alcohol derivative of the fluorinated olefin can be chemically oxidized with an oxidizing agent to the corresponding carboxylic acid.
  • oxidizing agents include for example potassium permanganate, chromium (VI) oxide, RuO 4 or OsO 4 optionally in the presence of NaOCl, nitric acid/iron catalyst, dinitrogen tetroxide.
  • the oxidation is carried out in acidic or basic conditions at a temperature between 10 and 100° C.
  • electrochemical oxidation may be used as well.
  • the fluorinated carboxylic acid corresponds to the following formula: R f b —(O) t —CFH—CF 2 —O—R-G (VII)
  • the R f b is selected from the group consisting of linear perfluorinated aliphatic groups of 1 to 6 carbon atoms, preferably having 1 to 4 carbon atoms, perfluorinated groups of the formula R f 1 —[OR f 2 ] p —[OR f 3 ] q — wherein R f 1 is a linear perfluorinated aliphatic group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, R f 2 and R f 3 each independently represents a linear perfluorinated alkylene of 1, 2, 3 or 4 carbon atoms and p and q each independently represent a value of 0 to 4 and wherein the sum of p and q is at least 1 and perfluorinated groups of the formula R f 4 —[OR f 5 ] k —[OR f 6 ] m —O—CF 2 — wherein R f 4 is a linear perfluorinated groups of the formula R f 4
  • Fluorinated carboxylic acids according to formula (VII) may be prepared through the preparation of an intermediate of formula (VIIa): R f b —(O) t —CFH—CF 2 —O—R-Z
  • the intermediate compound according to formula (VIIa) can be prepared by reacting a fluorinated olefin of the general formula (VIa) with an organic compound of the formula HO—R-Z (VIIb)
  • the amount of base can be upto 2 times the molar amount of the reactant of formula (VIIb).
  • the reaction is typically carried out in an aprotic solvent such as for example, tetrahydrofuran, acetonitrile, glyme, diglyme etc. Further suitable aprotic solvents are disclosed in DE 3828063.
  • the reaction is typically carried out a temperature between 0 and 200° C., for example between 10 and 150° C.
  • the reaction is generally carried out at an ambient pressure (1 bar) or up to 20 bar.
  • the resulting compound may be isolated and purified by distillation.
  • the fluorinated carboxylic acids of formula (VII) can be readily prepared by hydrolyzing the intermediate compound of formula (VIIa) above.
  • Z represents a carboxylic acid ester or a carboxylamide.
  • a carboxylic acid ester is used.
  • the ester can be an aliphatic ester, e.g. an alkyl ester in which the number of carbon atoms in the alkyl group are from 1 to 4.
  • Hydrolysis of the intermediate compound may be carried out under acidic or basic conditions and is generally carried out in an alcoholic acidic or basic solution of the intermediate compound.
  • L 1 represents a linear perfluorinated alkylene of 1, 2, 3, 4, 5 or 6 carbon atoms or a linear partially fluorinated alkylene having 1 to 6 carbon atoms and 1 or 2 hydrogen atoms
  • R f c is as defined in above formula (VIII) and AC represents a carboxylic acid group or salt thereof.
  • a particular example for L 1 includes a group of the formula —CFH—.
  • Particular compounds according to formula (IX) include those wherein R f c represents CF 3 CFH—.
  • Such groups can be obtained from decarboxylation of —CF(CF 3 )COOX groups (X is a cation) in the presence of a protic substance as described in JOC 34, 1841 (1969).
  • Fluorinated carboxylic acids of formula (VIII) are commercially available from Anles Ltd., St. Russia. These compounds may be prepared for example as described by Ershov and Popova in Fluorine Notes 4(11), 2002. Also, these fluorinated carboxylic acids typically form as byproducts in the manufacturing of hexafluoropropylene oxide by direct oxidation of hexafluoropropylene.
  • Fluorinated carboxylic acids according to formula (IX) can be derived from reactants that are also used in the manufacturing of fluorinated vinyl ethers as described in U.S. Pat. No. 6,255,536.
  • fluorinated carboxylic acids correspond to formula (XIII) CF 3 —CF 2 —O—R f h —COOX (XIII)
  • R f h representing a linear partially or fully fluorinated linear carbon chain of 1 to 8 carbon atoms optionally interrupted with one or more oxygen atoms, for example a perfluorinated linear aliphatic group of 1 to 6 carbon atoms, for example 1, 2, 3 or 4 carbon atoms and X is a monovalent cation.
  • Compounds of this formula can be made by conversion of diacid difluorides of formula (XIV) in the presence of e.g. antimony pentafluoride.
  • This conversion may be carried out at elevated temperature according to the method described in U.S. Pat. No. 3,555,100 resulting preferably in the decarbonylation of the secondary COF group.
  • the resulting mono acid fluoride can be converted to the corresponding salt using well known methods.
  • Fluorinated carboxylic acids having a —O—CF 2 —COOX group can be obtained from the corresponding vinyl ethers —O—CF ⁇ CF 2 .
  • Reaction of the vinyl ether with oxygen according to U.S. Pat. No. 4,987,254 results in acid fluorides carrying a —O—CF 2 COF group which can be readily converted to the corresponding acid or salt.
  • R f has the meaning as defined above in respect of generic formula (I). It is understood that while the above list of compounds only lists the acids, the corresponding salts, in particular the NH 4 + , potassium, sodium or lithium salts can equally be used.
  • Suitable adsorbent particles further include activated carbon, silica gel, clays and zeolites. Conveniently used are activated carbon particles.
  • the shape of the adsorbent particles is not particularly critical.
  • the adsorbent particles may have a plate shape, can be spherical, cylindrical or they can be rods. Also, adsorbent particles having a variety of different shapes may be used as a mixture.
  • the size of the adsorbent particles is typically between 0.05 mm and 20 mm, generally between 0.1 and 10 mm. A practical range is between 0.5 and 5 mm.
  • the adsorbent particles typically adsorb the fluorinated carboxylic acid on their surface and it will thus generally be preferred to optimize the specific surface area of the particles, i.e. the amount of surface per unit of weight.
  • the specific surface area of the adsorbent particles will be between 10 and 5000 m 2 /g, generally between 100 and 3000 m 2 /g with a practical range being from 300 to 2000 m 2 /g.
  • anion exchange resin particles can be used as adsorbent particles.
  • anion exchange resin that can be used to adsorb a fluorinated carboxylic acid include strong, medium strong as well as weak basic anion exchange resins.
  • strong, medium strong and weak basic anion exchange resin are defined in “Encyclopedia of Polymer Science and Engineering”, John Wiley & Sons, 1985, Volume 8, page 347 and “Kirk-Othmer”, John Wiley & Sons, 3 rd edition, Volume 13, page 687.
  • Strong basic anion exchange resin typically contain quaternary ammonium groups, medium strong resins usually have tertiary amine groups and weak basic resins usually have secondary amines as the anion exchange functions.
  • the fluorinated carboxylic acid may be recovered from strongly, medium strong or weak basic anion exchange resin particles.
  • strong, medium strong and weak basic anion exchange resin are defined in “Encyclopedia of Polymer Science and Engineering”, John Wiley & Sons, 1985, volume 8, page 347 and “Kirk-Othmer”, John Wiley & Sons, 3 rd edition, Volume 13, page 687.
  • Strong basic anion exchange resins typically contain quaternary ammonium groups, medium strong resins usually have tertiary amine groups and weak basic resins usually have secondary amines as the anion exchange functions.
  • Suitable eluting liquids for eluting the fluorinated carboxylic acids from basic anion exchange resin particles include a mixture of a mineral acid and a water miscible organic solvent.
  • Suitable mineral acids are all those the anions of which confer a salt form upon the anion exchanger (anion form) which is appropriate to the further adsorption of fluorinated emulsifying acids. Under the conditions of elution their oxidation strength should generally be so low that the anion exchanger will not be damaged oxidatively.
  • Mineral acids that can be used include, for example ortho-, meta-, and diphosphoric acid, nitric acid and preferably hydrochloric acid and sulfuric acid.
  • the eluting mixture for the elution of fluorinated carboxylic acid adsorbed to an anion exchange resin comprises a) water, b) a compound of the formula M-X in which M is an alkali metal or alkyl ammonium ion, and X is hydroxyl, fluoride or chloride, and c) at least one organic solvent capable of dissolving the other components a) and b) and thus provides a sufficient quantity of anions X for the elution of the fluorinated carboxylic acid from the anion exchanger resin.
  • the eluting liquid has the following composition:
  • Suitable solvents include those mentioned above.
  • Suitable cations M include lithium, sodium, potassium, tetramethylammonium and tetraethylammonium, and the preferred anion A is hydroxyl.
  • A represents an anion other than OH ⁇ and n equals the valence of A.
  • anions A include inorganic as well as organic anions.
  • Particular examples of inorganic anions include halogen or halogen containing inorganic anions such as for example F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , phosphates, sulfates, sulfonates, carbonates including HCO 3 ⁇ and CO 3 2 ⁇ .
  • organic anions include in particular carboxylic anions such as for example HCOO ⁇ and CH 3 COO ⁇ .
  • the amount of ammonium salt in the eluting liquid will generally depend on the nature of the anion exchange resin and the amount of fluorinated carboxylic acid adsorbed on the anion exchange resin and/or the percentage of recovery that is desired.
  • a suitable amount of ammonium salt is generally at least 0.1% by weight. According to a particular embodiment, the amount of ammonium salt is between 0.1 and 5% by weight based on the total weight of the composition used for eluting the exchange resin.
  • the amount of water miscible organic may vary widely but should generally be enough to dissolve the ammonium salt.
  • the amount of water-miscible organic solvent is generally at least 50% by weight of the total weight of the eluting composition. Exemplary ranges are 50 to 99.9% by weight, or between 60 and 90% by weight or between 90 and 98% by weight.
  • the eluting liquid comprising the ammonium salt and a water-miscible solvent may contain further components that may aid in the recovery of the fluorinated carboxylic acid from the anion exchange resin.
  • the eluting composition further comprises water. Water may for example be used in the eluting composition in an amount of up to 45% by weight, for example in an amount of 0.1 to 40% by weight or in amount between 1 and 15% by weight or in an amount between 4 and 10% by weight.
  • a further component that may be present in the eluting liquid is a base.
  • Suitable bases that may be used are alkali metal hydroxides such as for example sodium hydroxide and potassium hydroxide.
  • Other bases that may be used include earth alkali metal hydroxides, aluminium hydroxide or alcoholates such as for example sodium methylate.
  • the amount of base included in the composition is generally up to about 5% by weight.
  • An exemplary range is from 0.1 to 5% or from 0.5 to 2% by weight.
  • eluting liquids include those disclosed in U.S. Pat. No. 6,642,415 and EP 1,323,677.
  • the latter discloses eluting liquids comprising an alkaline mixture of water and an organic solvent.
  • An aqueous ammonia solution as disclosed in U.S. Pat. No. 3,882,153 may also be used.
  • the fluorinated carboxylic acid may be recovered by mixing the adsorbent particles (e.g. ion exchange resin or activated carbon) with an alcohol and optionally an acid. The mixture is then generally heated to cause esterification of the fluorinated carboxylic acid with the alcohol so as to form an ester derivative of the fluorinated carboxylic acid. The so obtained mixture may then be distilled to form a distillate comprising the ester derivative followed by separation of the ester derivative from the distillate. Generally, the eluting liquid will also comprise water.
  • adsorbent particles e.g. ion exchange resin or activated carbon
  • Suitable alcohols that may be used include in particular lower aliphatic alcohols having 1 to 5 carbon atoms such as methanol, ethanol and propanol. However aromatic alcohols may be used as well. Additionally, the alcohol may be added under the form of a precursor of the alcohol. Such a precursor should however form an alcohol under the conditions used to cause the esterification. Suitable precursors of the alcohol may include compounds such as ketals that readily form a corresponding alcohol under the acidic conditions existing in the eluting liquid or mixture thereof with the adsorbent particles.
  • the acid used with the eluting fluid is preferably an inorganic acid but the use of organic acids is not excluded.
  • the acid is preferably a strong acid such as for example sulphuric acid, hydrochloric acid, phosphoric acid or nitric acid.
  • the amount and nature of the acid used is typically such that a pH of less than 4, preferably not more than 3 and more preferably not more than 2 is attained in the mixture of eluting liquid and adsorbent particles.
  • the ester derivative may separate out as a separate phase, typically the lower phase, from the distillate.
  • the ester derivative can be easily separated from the distillate and the remainder of the distillate can be re-introduced into the mixture being distilled.
  • Such a circulating regeneration process thus allows a convenient regeneration of the adsorbent particles with a minimal amount of eluting fluid being needed.
  • the received ester can be further purified by distilllation and is then converted to the fluorinated acid salt by saponification typically with ammonia.
  • the eluated purified fluorinated carboxylic acid salt will typically have a purity sufficient to allow use of the compound in emulsion polymerization of fluorinated monomers.
  • the adsorbent particles can be regenerated several times before their efficiency drops below an uneconomical level at which point the adsorbent particles need to be disposed of.
  • the latex particle size determination was conducted by means of dynamic light scattering with a Malvern Zetazizer 1000 HAS in accordance to ISO/DIS 13321. Prior to the measurements, the polymer latexes as yielded from the polymerizations were diluted with 0.001 mol/L KCl-solution, the measurement temperature was 25° C. in all cases. The reported average is the Z-average particle diameter.
  • the polymerization experiments were performed in a 40 l kettle equipped with an impeller agitator and a baffle.
  • the kettle was charged with 30 l of deionized water and set to 35° C.; the kettle was evacuated repeatedly to remove oxygen; Agitation speed was set to 165 rpm.
  • the oxygen free kettle was charged with 70 mmol fluorinated emulsifier (unless specified differently) as listed in table 3 and the following materials were added: 0.5 ml of a solution containing 40 mg of copper sulphate penta hydrate and 1 mg of conc.
  • sulphuric acid 15 g of a 25 w-% of aqueous ammonia solution and 5.6 g of CF 3 CF 2 CF 2 —O—CF(CF 3 )—CF 2 —O—CF ⁇ CF 2 (PPVE-2).
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • Oxidation of perfluorinated vinyl ethers with oxygen in the presence of SbF 5 was carried out as described in U.S. Pat. No. 4,987,254.
  • the initially formed acid fluorides were esterified with methanol and purified by distillation.
  • the distilled esters were converted to the corresponding ammonium salts by saponification with aqueous ammonia.
  • a dry flask equipped with a magnetic stirrer bar, thermometer, dry ice reflux condenser, dropping funnel, and gas inlet tube was charged with 5 g of graphite.
  • the flask was flushed with nitrogen and 332 g of CF 3 OCF 2 CF 2 CF 2 OCF ⁇ CF 2 were added at room temperature.
  • the reflux condenser was replaced by a distillation device which allowed the separation of a lower phase while returning the upper phase to the flask.
  • Methanol 150 g was added and the mixture was heated for distillation. Distillation was carried out at ambient pressure without any intent for rectification. The condensed vapors separated into two phases. The lower phase was collected and the upper phase was returned to the flask. Distillation was continued until no more lower phase separated from the condensate.
  • the combined crude ester (493 g) was purified by fractionated distillation, resulting in 401 g CF 3 O(CF 2 ) 3 OCHFCOOCH 3 with a boiling point of 51 to 52° C./ 22 mbar. This corresponds to a yield of 78%, based on vinyl ether used.
  • the ester was converted to the ammonium salt by heating with aqueous ammonia and removal of methanol by fractionated distillation.
  • a 2 liter glass flask equipped with a thermometer, reflux condenser, dropping funnel and stirrer was used. 674 g water, 136 g KMnO4, and 38 g NaOH are placed in the flask. 169 g C 3 F 7 OCHFCF 2 CH 2 OH were added to the well stirred mixture via the dropping funnel. The temperature is held below 50° C. Residual permanganate was destroyed by addition of a small amount of methanol. The resulting slurry was filtered to remove the MnO 2 . After washing the filter cake with water, the combined filtrate was transferred to a distillation apparatus and acidified with 65 g of sulfuric acid. 100 g methanol was added and a flash distillation was started.
  • the ester was converted to the ammonium salt by saponification with aqueous ammonia and subsequent removal of methanol by distillation.
  • CH 3 —O—CF 2 —CF 2 —COOCH 3 was fluorinated as described in WO 01/46116; the acid fluoride CF 3 —O—CF 2 —CF 2 —COF was then converted into the methylester. The distilled ester was converted into the ammonia-salt as described above.
  • a sample of diacid fluoride, FCOCF(CF 3 )—O—(CF 2 ) 5 COF (500 g, 1.1 mol) prepared from the hexafluoropropylene oxide (HFPO) coupling of perfluoroadipoyl fluoride as described in U.S. Pub. No. 2004/0116742 and was added over 2 hours to a stirred slurry of sodium carbonate (500 g, 4.7 mol) in 500 g of diglyme at 85° C. to make the disalt. The reaction liberated CO 2 gas. Distilled water (25 g, 1.4 mol) was added at 85° C. The mixture was heated up to 168° C. with CO 2 off-gassing and held for 30 minutes.
  • HFPO hexafluoropropylene oxide
  • a mixture of 320 ml Tetrahydrofurane, 40 g Hydroxy acetic methylester and 188 g PPVE is cooled to 0° C., 27 g KOH-powder are added in small portions—during the addition of KOH, the reaction mixture heats up to 60° C. After the addition of KOH, the whole reaction mixture is agitated for 6 h at 25° C. The precipitated salt is separated by filtration, dissolved in 300 ml water and then treated with 57 g H 2 SO 4 (conc). The resulting mixture separates in two layers; the lower phase is C 3 F 7 —O—C 2 HF 3 —O—CH 2 —COOH, 86 g (56%). The distilled acid (bp. 125° C., 20 mbar) is neutralized with 25% aqueous ammonia solution to provide a 30% solution in water.
  • Compound C-2 was prepared as described in U.S. Pat. No. 6,703,520 (column 7).
  • the perfluorinated and partially fluorinated carboxylates were evaluated for urinary clearance using a pharmacokinetic study in rats. The goal was to measure the total amount of parent compound eliminated via urinary output and estimate the rate of elimination. The study was approved by the IACUC (Institutional Animal Care and Use Committees) and was performed in 3M Company's AAALAC (Association for Assessment and Accreditation of Laboratory Animal Care)—accredited facility.
  • the study utilized male Sprague Dawley rats, 6 to 8 weeks of age, and approximately 200 to 250 g body weight at study onset.
  • the concentration of the parent compound or metabolites thereof were quantitatively measured via fluorine NMR on each urine sample for each animal at each time point based on internally added standards.
  • T1 ⁇ 2 and % recovery are based on elimination of the major metabolite —C 3 F 7 —O—CHFCOO ⁇ .
  • regeneration solution 700 ml of a mixture of 60:20:20 wt-% of methanol:water: sulphuric acid (conc.) (herein called regeneration solution) was circulated for 6 hours through the column with a flow rate of about 1.4 l/h.
  • the regeneration solution was pumped from the top of a feeding tank through the column and back into the feeding tank (flow direction through the column from top to bottom).
  • the elution was done at room temperature.
  • phase separation occurred in the tank due to the formation of the corresponding ester (CF 3 O(CF 2 ) 3 OCF 2 COOCH 3 ).
  • the lower phase essentially consisting of the ester was separated.
  • the upper phase mainly containing methanol, water, sulphuric acid and residual ester, was distillated under atmospheric pressure.
  • the purified methanol contained residual amount of ester and was used for the next regeneration process.
  • the overall recovery efficiency calculated on ester was about 88%.
  • the regenerated ion-exchange resin could be re-used several times.

Abstract

A process for the recovery of fluorinated carboxylic acid or derivative thereof from adsorbent particles on which fluorinated carboxylic acid or a salt thereof is adsorbed. The process includes contacting the adsorbent particles with a liquid composition capable of removing at least part of the fluorinated carboxylic acid or salt thereof from the adsorbent particles. The fluorinated carboxylic acid or salt thereof is selected from the group consisting of fluorinated carboxylic acids or salts thereof that correspond to the general formula:
[RfO-L-COO]iXi+  (I)
wherein L represents a linear partially or fully fluorinated alkylene group or an aliphatic hydrocarbon group, Rf represents a linear partially or fully fluorinated aliphatic group or a linear partially or fully fluorinated aliphatic group interrupted with one or more oxygen atoms, Xi− represents a cation having the valence i and i is 1, 2 or 3.

Description

    CROSS-REFERENCE TO RELATED APPLICATION(S)
  • This application claims priority to Great Britain Application No. 0525978.3, filed on Dec. 21, 2005; Great Britain Application No. 0523853.0, filed on Nov. 24, 2005; Great Britain Application No. 0514398.7, filed on Jul. 15, 2005; and Great Britain Application No. 0514387.0 filed on Jul. 15, 2005, all of which are herein incorporated by reference in their entirety.
  • The present invention relates to the recovery of fluorinated carboxylic acids and derivatives thereof from adsorbent particles.
  • Polymerization of fluoroolefins to manufacture fluoropolymers, i.e. polymers having a fluorinated backbone, is often performed in aqueous media. In one such process referred to as emulsion polymerization, fluorinated carboxylic acids are typically used as surfactants in the aqueous media. Examples of these fluorosurfactants include the perfluorinated alkanecarboxylic acids having 7 to 10 carbon atoms, in particular perfluorooctanoic acid (PFOA). These acids are generally used in the salt form, preferably as ammonium salts. Fluoropolymerization to make “granular fluoropolymer” is also done in aqueous media in a process sometimes referred to as suspension polymerization, though with less fluorosurfactant (or none) than is used in dispersion polymerization. For a discussion of the processes, see “Tetrafluoroethylene Polymers” in the Encyclopedia of Polymer Science and Engineering, John Wiley & Sons, New York, 1989, Vol. 16, p. 580.
  • Because of its expense and to avoid undesirable release in the environment, the fluorosurfactant used in the polymerization processes is typically removed from the dispersions and waste streams generated in the manufacturing of the fluoropolymer, including waste waters and exhaust gas. An effective and frequently used method involves adsorbing the fluorosurfactant to adsorbent particles such as activated carbon and anion exchange resins. Such processes have been described in EP 1514848, EP 1093441, EP 1084097 and WO 2005/082785. Following the adsorption to the adsorbent particles, the fluorosurfactant is typically recovered there from using an eluting liquid as disclosed in for example EP 0014431, EP1069078, U.S. Pat. No. 6,642,415, EP 1323677 and U.S. Pat. No. 3,882,153.
  • These processes are typically practiced for recovering perfluorooctanoic acid or salts thereof, which is the most widely used surfactant in making fluoropolymers through aqueous emulsion polymerization. Unfortunately, these surfactants are eliminated only slowly from the body of living organisms and they hence show an undesirably high bioaccumulation. Notwithstanding the fact that these surfactants are recovered from the adsorbent particles, these processes themselves are disadvantages because operators of these processes may come into contact with the surfactants or derivatives thereof and hence special measures are typically necessary to avoid such contact or to at least minimize exposure of the operators to these compounds.
  • There was therefore a desire to find alternative surfactants that can be used in the making of fluoropolymer in aqueous emulsion polymerization and that can be recovered from adsorbent particles. It was in particular desirable to find alternative surfactants that eliminate faster from the body of living organisms and that thus have lower bioaccumulation than perfluorooctanoic acid or salts thereof.
  • In accordance with one aspect of the present invention, there is provided a process comprising recovery of fluorinated carboxylic acid or derivative thereof from adsorbent particles on which fluorinated carboxylic acid or a salt thereof is adsorbed, by contacting said adsorbent particles with a liquid composition capable of removing at least part of said fluorinated carboxylic acid or salt thereof from said adsorbent particles, wherein said fluorinated carboxylic acid or salt thereof is selected from the group consisting of fluorinated carboxylic acids or salts thereof that correspond to the general formula:
    [RfO-L-COO]iXi+  (I)
    wherein L represents a linear partially or fully fluorinated alkylene group or an aliphatic hydrocarbon group, Rf represents a linear partially or fully fluorinated aliphatic group or a linear partially or fully fluorinated aliphatic group interrupted with one or more oxygen atoms, Xi− represents a cation having the valence i and i is 1, 2 or 3.
  • It has been found that the fluorinated carboxylic acids or salts thereof according to formula (I) are suitable for making fluoropolymers by aqueous emulsion polymerization. These compounds can be removed from dispersions and waste streams by adsorbing them on adsorbent particles. They can furthermore be recovered from these adsorbent particles using a liquid composition capable of removing at least part of said fluorinated carboxylic acid or salt thereof from said adsorbent particles so that the fluorinated carboxylic acid can be re-used (after possible further purification) in the polymerization of fluorinated monomers. The fluorinated carboxylic acids or salts thereof typically have lower bioaccumulation than perfluorooctanoic acids or salts thereof and hence the elution process according to the invention provides advantages for the operators involved with the process.
  • By the term ‘liquid composition capable of removing at least part of said fluorinated carboxylic acid or salt thereof from said adsorbent particles’ is meant a liquid that is capable of dissolving and/or desorbing the fluorinated carboxylic acid and/or its salt or that alternatively converts the fluorinated carboxylic acid or salt into a derivative such as an ester that may be recovered from the mixture of adsorbent particles and the liquid. For sake of convenience, the liquid composition capable of removing at least part of said fluorinated carboxylic acid or salt thereof from said adsorbent particles will hereinafter be referred to as eluting liquid.
  • Fluorinated Carboxylic Acid
  • For the sake of convenience, the term ‘fluorinated carboxylic acid’ is hereinafter used to indicate the free acid as well as salts thereof. The fluorinated carboxylic acid used in the process of the invention corresponds to formula (I) above. Generally, the fluorinated carboxylic acid will be a low molecular weight compound, for example a compound having a molecular weight for the anion part of the compound of not more than 1000 g/mol, typically not more than 600 g/mol and in particular embodiments, the anion of the fluorinated carboxylic acid may have a molecular weight of not more than 500 g/mol.
  • Particularly preferred fluorinated carboxylic acids are those that when administered to rats show a recovery of at least 45%, for example at least 50% of the administered amount after 96 hours via renal elimination and that have a renal elimination half-life of not more than 35 hours, for example of not more than 30 hours in rats as tested according to the method set forth in the examples. Generally, fluorinated carboxylic acids in which each of the fluorinated aliphatic moieties in the compound have not more than 3 carbon atoms fulfill the aforementioned conditions of renal recovery and half-life. Thus, preferred compounds are those in which any fluorinated alkylene groups have not more than 3 carbon atoms and in which a fluorinated alkyl group of the compound has not more than 3 carbon atoms.
  • In the above formula (I), L represents a linking group. In one embodiment, the linking group can be a linear partially or fully fluorinated alkylene. Fully fluorinated alkylene groups include alkylene groups that consist of only carbon and fluorine atoms whereas partially fluorinated alkylene groups may additionally contain hydrogen. Generally, a partially fluorinated alkylene group should not contain more than 2 hydrogen atoms so as to be highly fluorinated and be non-telogenic or at least have minimal telogenic effects. Examples of fully fluorinated alkylene groups include linear perfluorinated alkylenes that have from 1 to 6 carbon atoms, for example linear perfluorinated alkylene groups of 1, 2, 3, 4 or 5 carbon atoms.
  • Examples of linear partially fluorinated alkylene groups include those that have from 1 to 6 carbon atoms. In a particular embodiment the linear partially fluorinated alkylene linking group has 1, 2, 3, 4, 5 or 6 carbon atoms and has only 1 or 2 hydrogen atoms. When the partially fluorinated alkylene group has 2 hydrogen atoms, they may be attached to the same carbon atom or they can be attached to different carbon atoms. When they are attached to different carbon atoms, such carbon atoms can be adjacent to each other or not. Also, in a particular embodiment, a carbon atom having 1 or 2 hydrogen atoms may be adjacent the ether oxygen atom to which the linking group is attached or adjacent the carboxylic group to which the linking group is attached at its other end.
  • In a further embodiment, the linking group L is an aliphatic hydrocarbon group. Examples of aliphatic hydrocarbon groups include linear, branched or cyclic aliphatic groups. Particular examples of aliphatic groups include linear or branched alkylene groups of 1 to 4 carbon atoms such as for example methylene or ethylene.
  • Particular examples of linking groups L may be selected from the following:
  • —(CF2)g— wherein g is 1, 2, 3, 4, 5 or 6;
  • —CFH—(CF2)h— wherein h is 0, 1, 2, 3, 4 or 5;
  • —CF2—CFH—(CF2)d— wherein d is 0, 1, 2, 3 or 4;
  • —CH2—(CF2)h— wherein h is 1, 2, 3 or 4;
  • —(CH2)c— wherein c is 1, 2, 3 or 4;
  • In the above examples, the left side of the formula of the linking group is the site where the linking group is connected to the ether oxygen in formula (I).
  • The Rf group in formula (I) represents a linear partially or fully fluorinated aliphatic group or a linear partially or fully fluorinated aliphatic group interrupted with one or more oxygen atoms. In one embodiment, Rf is a linear perfluorinated aliphatic group having 1 to 6 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms. According to another embodiment Rf is a linear perfluorinated aliphatic group interrupted with one or more oxygen atoms of which the alkylene groups between oxygen atoms have not more than 4 or 6 carbon atoms, for example 3 or less carbon atoms and wherein the terminal alkyl group has not more than 4 or 6 carbon atoms, for example 3 or less carbon atoms. According to a still further embodiment, Rf is a linear partially fluorinated aliphatic group having 1 to 6 carbon atoms and not more than 2 hydrogen atoms or a linear partially fluorinated aliphatic group interrupted with one or more oxygen atoms and which has not more than 2 hydrogen atoms. In the latter embodiment, it will generally be preferred that any perfluorinated alkylene moiety has not more than 4 or 6 carbon atoms and any terminal perfluorinated alkyl group, likewise preferably should not have more than 6 carbon atoms, for example not more than 4 carbon atoms. A particular example of a partially fluorinated aliphatic group Rf is CF3CFH—.
  • In a particular embodiment, Rf may correspond to the following formula:
    Rf 1—[ORf 2]p—[ORf 3]q—  (II)
  • wherein Rf 1 is a perfluorinated linear aliphatic group of 1 to 6 carbon atoms (for example 3 or less), Rf 2 and Rf 3 each independently represents a linear perfluorinated alkylene of 1, 2, 3 or 4 carbon atoms and p and q each independently represent a value of 0 to 4 and wherein the sum of p and q is at least 1.
  • In another embodiment, Rf may correspond to the following formula:
    R7 f—(O)t—CFH—CF2—  (III)
  • wherein t is 0 or 1 and R7 f represents a linear partially or fully fluorinated aliphatic group optionally interrupted with one or more oxygen atoms. Typically R7 f does not contain perfluorinated aliphatic moieties of more than 4 or 6 carbon atoms. For example, in one embodiment, R7 f is a perfluorinated linear aliphatic group of 1 to 6 carbon atoms. In another embodiment, R7 f is a group corresponding to above formula (II).
  • In yet a further embodiment, Rf may correspond to the following formula:
    Rf 1—(OCF2)a—  (IV)
  • wherein a is an integer of 1 to 6 and Rf 8 is a linear partially fluorinated aliphatic group or a linear fully fluorinated aliphatic group having 1, 2, 3 or 4 carbon atoms. When Rf 8 is a partially fluorinated aliphatic group, the number of carbon atoms preferably is between 1 and 6 and the number of hydrogen atoms in the partially fluorinated aliphatic groups is preferably 1 or 2.
  • In a still further embodiment, Rf may correspond to the following formula:
    Rf 9—O—(CF2)b—  (V)
  • wherein b is an integer of 1 to 6, preferably 1, 2, 3 or 4 and Rf 9 is a linear partially fluorinated aliphatic group or a linear fully fluorinated aliphatic group having 1, 2, 3 or 4 carbon atoms. When Rf 9 is a partially fluorinated aliphatic group, the number of carbon atoms preferably is between 1 and 6 and the number of hydrogen atoms in the partially fluorinated groups is preferably 1 or 2.
  • In a particular embodiment of the present invention, the fluorinated carboxylic acid corresponds to the following formula:
    [Rf a—(O)t—CHF—(CF2)n—COO]iXi+  (VI)
  • wherein Rf a represents a linear partially or fully fluorinated aliphatic group optionally interrupted with one or more oxygen atoms, t is 0 or 1 and n is 0 or 1, Xi+ represents a cation having a valence i and i is 1, 2 or 3, with the proviso that when t is 0, the Rf a contains at least one ether oxygen atom.
  • In a particular aspect of this embodiment, the Rf a is selected from the group consisting of linear perfluorinated aliphatic groups of 1 to 6 carbon atoms, preferably having 1 to 4 carbon atoms, perfluorinated groups of the formula Rf 1—[ORf 2]p—[ORf 3]q— wherein Rf 1 is a linear perfluorinated aliphatic group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, Rf 2 and Rf 3 each independently represents a linear perfluorinated alkylene of 1, 2, 3 or 4 carbon atoms and p and q each independently represent a value of 0 to 4 and wherein the sum of p and q is at least 1 and perfluorinated groups of the formula Rf 4—[ORf 5]k—[ORf 6]m—O—CF2— wherein Rf 4 is a linear perfluorinated aliphatic group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, Rf 5 and Rf 6 each independently represents a linear perfluorinated alkylene of 1, 2, 3 or 4 carbon atoms and k and m each independently represent a value of 0 to 4.
  • Fluorinated carboxylic acid of formula (VI) can be derived from fluorinated olefins of the general formula:
    Ra f—(O)t—CF═CF2   (VIa)
  • wherein Ra f and t are as defined above. Compounds according to formula (VIa) are well known in the art and include fluorinated olefins such as perfluorinated alkyl vinyl compounds, vinyl ethers in particular perfluorovinyl ethers and allyl ethers, in particular perfluorinated allyl ethers.
  • Fluorinated carboxylic acids according to formula (VI) wherein n is 0 can be prepared by reacting a fluorinated olefin of formula (VIa) with a base. The reaction is generally carried out in aqueous media. An organic solvent may be added to improve the solubility of the fluorinated olefin. Examples of organic solvents include glyme, tetrahydrofuran (THF) and acetonitrile. Additionally or alternatively a phase transfer catalyst may be used. As a base, use can be made of for example ammonia, alkali and earth alkali hydroxides. Without intending to be bound by any theory, it is believed, that the reaction proceeds according to the following sequence when ammonia is used as a base:
    Rf—(O)t—CF═CF2+NH3+H2O→Rf—(O)t—CHF—COONH4+NH4F
  • The reaction is generally carried out between 0 and 200° C., for example between 20-150° C. and at a pressure between about 1 bar up to about 20 bar. For further purification, the obtained salts can be distilled via the free acid or by first converting the acid into an ester derivative and then distilling the ester derivative followed by hydolysis of the ester to obtain the purified acid or salt thereof.
  • Fluorinated carboxylic acids of formula (VI) wherein n is 0 can also be prepared by reacting a fluorinated olefin of formula (VIa) with a hydrocarbon alcohol in an alkaline medium and then decomposing the resulting ether in acidic conditions thereby forming the corresponding carboxylic acid. Suitable hydrocarbon alcohols include aliphatic alcohols such as lower alkanols having 1 to 4 carbon atoms. Specific examples include methanol, ethanol and butanol including t-butanol. The reaction of the fluorinated olefin with the alcohol in an alkaline medium may be carried out as described in “Furin et al., Bull Korean Chem. Soc. 20, 220 (1999)”. The reaction product of this reaction is an ether derivative of the fluorinated olefin. This resulting ether can be decomposed under acidic conditions as described in “D. C. England, J. Org. Chem. 49, 4007 (1984)” to yield the corresponding carboxylic acid or salt thereof.
  • To prepare fluorinated carboxylic acids of formula (VI) wherein n is 1, a free radical reaction of the fluorinated olefin of formula (VIa) with methanol may be carried out followed by an oxidation of the resulting reaction product. The free radical reaction is typically carried out using a free radical initiator as is typically used in a free radical polymerization reaction. Examples of suitable free radical initiators include persulfates such as for example ammonium persulfate. Detailed conditions of the free radical reaction of the fluorinated carboxylic acid with an alcohol can be found in “S. V. Sokolov et al., Zh. Vses. Khim Obsh 24, 656 (1979)”. The resulting alcohol derivative of the fluorinated olefin can be chemically oxidized with an oxidizing agent to the corresponding carboxylic acid. Examples of oxidizing agents include for example potassium permanganate, chromium (VI) oxide, RuO4 or OsO4 optionally in the presence of NaOCl, nitric acid/iron catalyst, dinitrogen tetroxide. Typically the oxidation is carried out in acidic or basic conditions at a temperature between 10 and 100° C. In addition to chemical oxidation, electrochemical oxidation may be used as well.
  • In another embodiment, the fluorinated carboxylic acid corresponds to the following formula:
    Rf b—(O)t—CFH—CF2—O—R-G   (VII)
  • wherein Rf b represents a linear partially or fully fluorinated aliphatic group optionally interrupted with one or more oxygen atoms, R is an aliphatic hydrocarbon group, G represents a carboxylic acid or salt thereof, t is 0 or 1. Particular examples for R include a methylene group or an ethylene group.
  • In a particular aspect of this embodiment, the Rf b is selected from the group consisting of linear perfluorinated aliphatic groups of 1 to 6 carbon atoms, preferably having 1 to 4 carbon atoms, perfluorinated groups of the formula Rf 1—[ORf 2]p—[ORf 3]q— wherein Rf 1 is a linear perfluorinated aliphatic group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, Rf 2 and Rf 3 each independently represents a linear perfluorinated alkylene of 1, 2, 3 or 4 carbon atoms and p and q each independently represent a value of 0 to 4 and wherein the sum of p and q is at least 1 and perfluorinated groups of the formula Rf 4—[ORf 5]k—[ORf 6]m—O—CF2— wherein Rf 4 is a linear perfluorinated aliphatic group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, Rf 5 and Rf 6 each independently represents a linear perfluorinated alkylene of 1, 2, 3 or 4 carbon atoms and k and m each independently represent a value of 0 to 4.
  • Fluorinated carboxylic acids according to formula (VII) may be prepared through the preparation of an intermediate of formula (VIIa):
    Rf b—(O)t—CFH—CF2—O—R-Z
  • wherein Rf b, t and R have the same meaning as defined above. Z represents a carboxylic acid ester or a carboxylamide.
  • The intermediate compound according to formula (VIIa) can be prepared by reacting a fluorinated olefin of the general formula (VIa) with an organic compound of the formula
    HO—R-Z   (VIIb)
  • wherein Z and R are as defined above. Compounds according to formula (VIIb) are well known in the art and/or are commercially available. The reaction of compound (VIa) with compound (VIIb) is typically carried out in the presence of a base although it is also possible to carry out the reaction under acidic or neutral conditions. Suitable bases include carbonates such as potassium carbonate, sodium carbonate and lithium carbonate, hydroxides, alkoholates etc. The amount of base used may vary widely. For example a catalytic amount may be used. Generally the amount of base used will be about at least 1 or 2% by weight based on the amount of reactant of formula (VIIb). In a particular embodiment, the amount of base can be upto 2 times the molar amount of the reactant of formula (VIIb). The reaction is typically carried out in an aprotic solvent such as for example, tetrahydrofuran, acetonitrile, glyme, diglyme etc. Further suitable aprotic solvents are disclosed in DE 3828063. The reaction is typically carried out a temperature between 0 and 200° C., for example between 10 and 150° C. The reaction is generally carried out at an ambient pressure (1 bar) or up to 20 bar. Following the reaction, the resulting compound may be isolated and purified by distillation.
  • The fluorinated carboxylic acids of formula (VII) can be readily prepared by hydrolyzing the intermediate compound of formula (VIIa) above. In formula (VIIa) above, Z represents a carboxylic acid ester or a carboxylamide. Typically a carboxylic acid ester is used. In one embodiment, the ester can be an aliphatic ester, e.g. an alkyl ester in which the number of carbon atoms in the alkyl group are from 1 to 4. Hydrolysis of the intermediate compound may be carried out under acidic or basic conditions and is generally carried out in an alcoholic acidic or basic solution of the intermediate compound. Alternatively the intermediate compound may be hydrolysed in an acidic or basic solution of other water miscible organic solvents such as ketones, ethers etc. Typically, a basic alcoholic solution is used such as for example a methanol or ethanol solution containing an alkali metal hydroxide as the base. Typically the hydrolysis is carried out at room temperature but it is also possible to use elevated temperatures of for example up to the boiling point of the solution.
  • Alternatively, the fluorinated surfactant may be prepared by reacting the fluorinated olefin of formula (VIa) above with a hydroxy substituted carboxylic acid or salt thereof.
  • Thus, in accordance with this embodiment the fluorinated olefin of formula (VIa) is reacted with a compound of the formula:
    HO—R-G   (VIc)
  • wherein G is a carboxylic acid group or salt thereof and R is as defined above. The reaction of a fluorinated olefin of formula (VIa) with a hydroxy compound or formula (VIIc) can be carried out under the same conditions described above for the reaction with compounds of formula (VIIb).
  • In a still further embodiment, the fluorinated carboxylic acid corresponds to one of the following formulas:
    Rf c—(OCF2)u—O—(CF2)v-AC   (VIII)
  • wherein u is an integer of 1 to 6, v is an integer of 1 to 6, Rf c represents a linear perfluorinated aliphatic group of 1, 2, 3 or 4 carbon atoms and AC represents a carboxylic acid group or salt thereof, and
    Rf c—O—(CF2)y—O-L1-AC   (IX)
  • wherein y has a value of 1, 2, 3, 4, 5 or 6, L1 represents a linear perfluorinated alkylene of 1, 2, 3, 4, 5 or 6 carbon atoms or a linear partially fluorinated alkylene having 1 to 6 carbon atoms and 1 or 2 hydrogen atoms, Rf c is as defined in above formula (VIII) and AC represents a carboxylic acid group or salt thereof. A particular example for L1 includes a group of the formula —CFH—. Particular compounds according to formula (IX) include those wherein Rf c represents CF3CFH—. Such groups can be obtained from decarboxylation of —CF(CF3)COOX groups (X is a cation) in the presence of a protic substance as described in JOC 34, 1841 (1969).
  • Fluorinated carboxylic acids of formula (VIII) are commercially available from Anles Ltd., St. Petersburg, Russia. These compounds may be prepared for example as described by Ershov and Popova in Fluorine Notes 4(11), 2002. Also, these fluorinated carboxylic acids typically form as byproducts in the manufacturing of hexafluoropropylene oxide by direct oxidation of hexafluoropropylene.
  • Fluorinated carboxylic acids according to formula (IX) can be derived from reactants that are also used in the manufacturing of fluorinated vinyl ethers as described in U.S. Pat. No. 6,255,536.
  • In another embodiment acid fluorides of formula (X) are reacted with a metal fluoride like KF or CsF:
    Rf g—COF   (X)
  • wherein Rf g is a partially or perfluorinated linear aliphatic chain optionally interrupted with one or more oxygen atoms. This reaction results in an alkoxylate that can be further reacted with a carboxylic acid derivative of formula (XI)
    Y—(CH2)n-Q   (XI)
  • wherein Y represents a leaving group like iodide, bromide, chloride, mesylate, tosylate and the like, n is an integer from 1 to 3, and Q represents a carboxyl acid group or a lower alkyl ester. The reaction results in fluorinated carboxylic acid derivatives of formula (XII)
    Rf g—CF2—O—(CH2)nQ   (XII)
  • with Rf g n, and Q having the same meaning as above. The corresponding salts can be obtained by saponification.
  • In yet a further embodiment the fluorinated carboxylic acids correspond to formula (XIII)
    CF3—CF2—O—Rf h—COOX   (XIII)
  • with Rf h representing a linear partially or fully fluorinated linear carbon chain of 1 to 8 carbon atoms optionally interrupted with one or more oxygen atoms, for example a perfluorinated linear aliphatic group of 1 to 6 carbon atoms, for example 1, 2, 3 or 4 carbon atoms and X is a monovalent cation. Compounds of this formula can be made by conversion of diacid difluorides of formula (XIV) in the presence of e.g. antimony pentafluoride.
    FOC—CF(CF3)—O—Rf h—COF   (XIV)
  • This conversion may be carried out at elevated temperature according to the method described in U.S. Pat. No. 3,555,100 resulting preferably in the decarbonylation of the secondary COF group. The resulting mono acid fluoride can be converted to the corresponding salt using well known methods.
  • Fluorinated carboxylic acids having a —O—CF2—COOX group can be obtained from the corresponding vinyl ethers —O—CF═CF2. Reaction of the vinyl ether with oxygen according to U.S. Pat. No. 4,987,254 results in acid fluorides carrying a —O—CF2COF group which can be readily converted to the corresponding acid or salt.
  • Specific examples of compounds according to formula (I) include the following:
  • Rf—O—CHF—COOH
  • C3F7—O—CHF—COOH
  • CF3—O—CF2CF2—CF2—O—CHF—COOH
  • CF3CF2CF2—O—CF2CF2—CF2—O—CHF—COOH
  • CF3—O—CF2—CF2—O—CHF—COOH
  • CF3—O—CF2—O—CF2—CF2—O—CHF—COOH
  • CF3—(O—CF2)2—O—CF2—CF2—O—CHF—COOH
  • CF3—(O—CF2)3—O—CF2—CF2—O—CHF—COOH
  • Rf—O—CHF—CF2—COOH
  • CF3—O—CHF—CF2—COOH
  • CF3—O—CF2—CF2—O—CHF—CF2—COOH
  • CF3—CF2—O—CHF—CF2—COOH
  • CF3—O—CF2—F2—CF2—O—CHF—CF2—COOH
  • CF3—O—CF2—O—CF2—CF2—O—CHF—CF2—COOH
  • CF3—(O—CF2)2—O—CF2—CF2—O—CHF—CF2—COOH
  • CF3—(O—CF2)3—O—CF2—CF2—O—CHF—CF2—COOH
  • Rf—O—CF2—CHFCOOH
  • CF3—O—CF2—CHF—COOH
  • C3F7—O—CF2—CHF—COOH
  • CF3—O—CF2—CF2—CF2—O—CF2—CHF—COOH
  • CF3—O—CF2—O—CF2—CF2—O—CF2—CHF—COOH
  • CF3—(O—CF2)2—O—CF2—CF2—O—CF2—CHF—COOH
  • CF3—(O—CF2)3—O—CF2—CF2—O—CF2—CHF—COOH
  • Rf—O—CF2—CHF—CF2COOH
  • CF3—O—CF2—CHF—CF2—COOH
  • C2F5—O—CF2—CHF—CF2—COOH
  • C3F7—O—CF2—CHF—CF2—COOH
  • CF3—O—CF2—CF2—CF2—O—CF2—CHF—CF2—COOH
  • CF3—O—CF2—O—CF2—CF2—O—CF2—CHF—CF2—COOH
  • CF3—(O—CF2)2—O—CF2—CF2—O—CF2—CHF—CF2—COOH
  • CF3—(O—CF2)3—O—CF2—CF2—O—CF2—CHF—CF2—COOH
  • Rf—(O)m—CHF—CF2—O—(CH2)n—COOH n=1,2 or 3; m=0 or 1
  • CF3—O—CHF—CF2—O—CH2—COOH
  • CF3—O—CF2—CF2—CF2—O—CHF—CF2—O—CH2—COOH
  • C3F7—O—CHF—CF2—O—CH2—COOH
  • C3F7—O—CHF—CF2—O—CH2—CH2—COOH
  • C3F7—O—CF2—CF2—O—CHF—CF2—OCH2COOH
  • C3F7—O—CF2—CF2—CF2—O—CHF—CF2—OCH2COOH
  • C3F7—O—CF2—CHF—CF2—OCH2COOH
  • CF3—CHF—CF2—O—CH2COOH
  • C3F7—CF2—CHF—CF2—OCH2—COOH
  • CF3—O—CF2—CF2—O—CH2—COOH
  • CF3—O—CF2—CF2—CF2—O—CF2—CF2—O—CH2—COOH
  • C3F7—O—CF2—CF2—O—CH2—COOH
  • C3F7—O—CF2—CF2—O—CH2—CH2—COOH
  • C3F7—O—CF2—CF2—O—CF2—CF2—OCH2COOH
  • C3F7—O—CF2—CF2—CF2—O—CF2-CF2—OCH2COOH
  • C3F7—O—CF2—CF2—CF2—OCH2COOH
  • C4F9—O—CH2—COOH
  • C4F9—O—CH2—CH2—COOH
  • C3F7—O—CH2COOH
  • C6F13—OCH2—COOH
  • Rf—O—CF2—CF2—COOH
  • CF3—O—CF2—CF2—COOH
  • C2F5—O—CF2—CF2—COOH
  • C3F7—O—CF2—CF2—COOH
  • C4F9—O—CF2—CF2—COOH
  • Rf—(O—CF2)u—O—CF2—COOH with u being as defined above
  • CF3—(O—CF2)3—O—CF2—COOH
  • CF3—(O—CF2)2—O—CF2—COOH
  • CF3—(O—CF2)1—O—CF2—COOH
  • Rf—(O—CF2—CF2)k—O—CF2—COOH with k being 1, 2 or 3
  • CF3—(O—CF2—CF2)1—O—CF2—COOH
  • C2F5—(O—CF2—CF2)1—O—CF2—COOH
  • C3F7—(O—CF2—CF2)1—O—CF2—COOH
  • C4F9—(O—CF2—CF2)1—O—CF2—COOH
  • C2F5—(O—CF2—CF2)2—O—CF2—COOH
  • CF3—(O—CF2—CF2)2—O—CF2—COOH
  • C3F7—(O—CF2—CF2)2—O—CF2—COOH
  • C4F9—(O—CF2—CF2)2—O—CF2—COOH
  • Rf—O—CF2—COOH
  • C3F7—O—CF2—COOH
  • CF3—O—CF2—CF2—CF2—O—CF2—COOH
  • CF3—CHF—O—(CF2)o—COOH with o being an integer of 1, 2, 3, 4, 5 or 6
  • CF3CFH—O—(CF2)3—COOH
  • CF3CFH—O—(CF2)5—COOH
  • CF3—CF2—O—(CF2)o—COOH with o being as above
  • CF3—CF2—O—(CF2)3COOH
  • CF3—CF2—O—(CF2)5COOH
  • In the above generic formulas, Rf has the meaning as defined above in respect of generic formula (I). It is understood that while the above list of compounds only lists the acids, the corresponding salts, in particular the NH4 +, potassium, sodium or lithium salts can equally be used.
  • Adsorbent Particles
  • By the term ‘absorbent particles’ in connection with the present invention is meant particles that are capable of physically adsorbing the fluorinated carboxylic acid or salt thereof by whatever mechanism of physical adsorption including but not limited to ionic interactions causing physical adsorption. Accordingly, the term ‘adsorbent particles’ include ion exchange resins, which typically bind fluorinated carboxylic acids, which have ionic groups, as a result of an ion exchange process although the adsorption to the exchange resin may also occur by a physical adsorption process other than the ion exchange process.
  • Suitable adsorbent particles further include activated carbon, silica gel, clays and zeolites. Conveniently used are activated carbon particles. The shape of the adsorbent particles is not particularly critical. For example, the adsorbent particles may have a plate shape, can be spherical, cylindrical or they can be rods. Also, adsorbent particles having a variety of different shapes may be used as a mixture. The size of the adsorbent particles is typically between 0.05 mm and 20 mm, generally between 0.1 and 10 mm. A practical range is between 0.5 and 5 mm. The adsorbent particles typically adsorb the fluorinated carboxylic acid on their surface and it will thus generally be preferred to optimize the specific surface area of the particles, i.e. the amount of surface per unit of weight. Typically, the specific surface area of the adsorbent particles will be between 10 and 5000 m2/g, generally between 100 and 3000 m2/g with a practical range being from 300 to 2000 m2/g.
  • Additionally, anion exchange resin particles can be used as adsorbent particles. Examples of anion exchange resin that can be used to adsorb a fluorinated carboxylic acid include strong, medium strong as well as weak basic anion exchange resins. The terms strong, medium strong and weak basic anion exchange resin are defined in “Encyclopedia of Polymer Science and Engineering”, John Wiley & Sons, 1985, Volume 8, page 347 and “Kirk-Othmer”, John Wiley & Sons, 3rd edition, Volume 13, page 687. Strong basic anion exchange resin typically contain quaternary ammonium groups, medium strong resins usually have tertiary amine groups and weak basic resins usually have secondary amines as the anion exchange functions. Examples of anion exchange resins that are commercially available for use in this invention include AMBERLITE® IRA-402, AMBERJET® 4200, AMBERLITE® IRA-67 and AMBERLITE® IRA-92 all available from Rohm & Haas, PUROLITE® A845 (Purolite GmbH) and LEWATIT® MP-500 (Bayer AG).
  • Eluting Liquid
  • The fluorinated carboxylic acids that are adsorbed on an adsorbent particle may be recovered therefrom by eluting the loaded adsorbent particles with an eluting liquid capable of desorbing and/or dissolving the fluorinated carboxylic acid or a derivative thereof. The nature and composition of the eluting liquid typically depends on the nature of the adsorbent particles to which the fluorinated carboxylic acid is adsorbed and typically includes an organic solvent. Also, the recovery or elution of the adsorbent particles may be practiced over a wide range of temperature. For example, in one embodiment, the recovery is practiced at ambient temperature, i.e. between 10 and 35° C. In another embodiment, the recovery may be carried out at elevated temperature of for example 40° C. or more up to in certain embodiments the boiling point of the eluting liquid.
  • In one embodiment, the fluorinated carboxylic acid may be recovered from strongly, medium strong or weak basic anion exchange resin particles. The terms strong, medium strong and weak basic anion exchange resin are defined in “Encyclopedia of Polymer Science and Engineering”, John Wiley & Sons, 1985, volume 8, page 347 and “Kirk-Othmer”, John Wiley & Sons, 3rd edition, Volume 13, page 687. Strong basic anion exchange resins typically contain quaternary ammonium groups, medium strong resins usually have tertiary amine groups and weak basic resins usually have secondary amines as the anion exchange functions.
  • Suitable eluting liquids for eluting the fluorinated carboxylic acids from basic anion exchange resin particles include a mixture of a mineral acid and a water miscible organic solvent. Suitable mineral acids are all those the anions of which confer a salt form upon the anion exchanger (anion form) which is appropriate to the further adsorption of fluorinated emulsifying acids. Under the conditions of elution their oxidation strength should generally be so low that the anion exchanger will not be damaged oxidatively. Mineral acids that can be used include, for example ortho-, meta-, and diphosphoric acid, nitric acid and preferably hydrochloric acid and sulfuric acid.
  • Suitable organic solvents include polar organic solvents such as alcohols, aliphatic or aromatic ethers, nitrites, amides, sulfoxides, ketones and carboxylic acid esters. Preferred solvents include those that are substantially miscible with water, i.e. miscible to at least 40% by volume when mixing equal volumes, or solvents that are completely miscible with water. Solvents of this type are especially aliphatic alcohols having from 1 to 4 carbon atoms, preferably methanol and ethanol, as well as mono- and dimethyl ethers and mono- and diethyl ethers of ethylene glycol or of the corresponding monoethers of polyglycols having a chain length up to that of decaethylene glycol. It is likewise possible to use mixtures of the aforesaid solvents.
  • A typical eluting liquid may be prepared from the mineral acid and the organic solvent to be used the acid concentration of which, calculated on the total mixture, is adjusted in the range of from 0.5 to 10 N, preferably 0.5 to 2 N. In said mixture the proportion of mineral acid (including the water portion) to solvent ranges from 1:0.25 to 1:20, preferably 1:3 to 1:10 parts by volume.
  • For a quantitative elution of the adsorbed fluorinated carboxylic acids 50 to 500 and preferably 100 to 225 parts by volume, calculated on 100 parts of anion exchanger matrix, of the mixture of mineral acid and organic solvent is typically used.
  • When the elution is terminated the eluate generally separates into two layers of which the lower layer having the higher specific gravity contains approximately the entire amount of fluorinated carboxylic acid. The lower layer may be neutralized with dilute, usually 2 N sodium hydroxide solution and the fluorinated carboxylic acid is typically precipitated in compact form and easy to separate by adding the neutralized phase while stirring to dilute hydrochloric acid.
  • In another embodiment, the eluting mixture for the elution of fluorinated carboxylic acid adsorbed to an anion exchange resin comprises a) water, b) a compound of the formula M-X in which M is an alkali metal or alkyl ammonium ion, and X is hydroxyl, fluoride or chloride, and c) at least one organic solvent capable of dissolving the other components a) and b) and thus provides a sufficient quantity of anions X for the elution of the fluorinated carboxylic acid from the anion exchanger resin.
  • In a particular aspect of this embodiment, the eluting liquid has the following composition:
      • a) from 15 to 40% of water,
      • b) from 1 to 10 of the compound M-A, and
      • c) from 60 to 70% of the solvent.
  • In another aspect, the eluting mixture has the following composition:
  • a) from 18 to 35% of water,
  • b) from 2 to 8% of M-A, and
  • c) from 60 to 70% of solvent.
  • Useful solvents include those mentioned above. Suitable cations M include lithium, sodium, potassium, tetramethylammonium and tetraethylammonium, and the preferred anion A is hydroxyl.
  • In yet a further embodiment, the fluorinated carboxylic acid may be recovered from a strongly basic anion exchange resin using an eluting liquid comprising an ammonium salt and a water miscible organic solvent. The ammonium salt is typically one that corresponds to the general formula:
    (NH4)nA
  • wherein A represents an anion other than OH and n equals the valence of A. Examples of anions A include inorganic as well as organic anions. Particular examples of inorganic anions include halogen or halogen containing inorganic anions such as for example F, Cl, Br, I, ClO4 , phosphates, sulfates, sulfonates, carbonates including HCO3 and CO3 2−. Examples of organic anions include in particular carboxylic anions such as for example HCOO and CH3COO.
  • The amount of ammonium salt in the eluting liquid will generally depend on the nature of the anion exchange resin and the amount of fluorinated carboxylic acid adsorbed on the anion exchange resin and/or the percentage of recovery that is desired. A suitable amount of ammonium salt is generally at least 0.1% by weight. According to a particular embodiment, the amount of ammonium salt is between 0.1 and 5% by weight based on the total weight of the composition used for eluting the exchange resin.
  • The eluting composition further includes a water-miscible solvent. By ‘water miscible solvent’ is generally meant an organic solvent that has solubility in water of at least 5% by weight, for example at least 10% by weight or at least 20% by weight. Suitable water-miscible solvents are typically polar solvents including for example alcohols, ketones, ethers and mixtures thereof Particular examples of solvents include lower alkanols having between 1 and 6 carbon atoms such as for example methanol, ethanol and propanol; glycols, mono- and dialkyl ethers or monoglycol and diglycol wherein the alkyl groups have between 1 and 4 carbon atoms; ketones such as acetone and methyl ethyl ketone. The amount of water miscible organic may vary widely but should generally be enough to dissolve the ammonium salt. The amount of water-miscible organic solvent is generally at least 50% by weight of the total weight of the eluting composition. Exemplary ranges are 50 to 99.9% by weight, or between 60 and 90% by weight or between 90 and 98% by weight.
  • The eluting liquid comprising the ammonium salt and a water-miscible solvent may contain further components that may aid in the recovery of the fluorinated carboxylic acid from the anion exchange resin. In one particular embodiment, the eluting composition further comprises water. Water may for example be used in the eluting composition in an amount of up to 45% by weight, for example in an amount of 0.1 to 40% by weight or in amount between 1 and 15% by weight or in an amount between 4 and 10% by weight.
  • A further component that may be present in the eluting liquid is a base. Suitable bases that may be used are alkali metal hydroxides such as for example sodium hydroxide and potassium hydroxide. Other bases that may be used include earth alkali metal hydroxides, aluminium hydroxide or alcoholates such as for example sodium methylate. When present, the amount of base included in the composition is generally up to about 5% by weight. An exemplary range is from 0.1 to 5% or from 0.5 to 2% by weight.
  • Further eluting liquids include those disclosed in U.S. Pat. No. 6,642,415 and EP 1,323,677. The latter discloses eluting liquids comprising an alkaline mixture of water and an organic solvent. An aqueous ammonia solution as disclosed in U.S. Pat. No. 3,882,153 may also be used.
  • According to a further embodiment, the fluorinated carboxylic acid may be recovered by mixing the adsorbent particles (e.g. ion exchange resin or activated carbon) with an alcohol and optionally an acid. The mixture is then generally heated to cause esterification of the fluorinated carboxylic acid with the alcohol so as to form an ester derivative of the fluorinated carboxylic acid. The so obtained mixture may then be distilled to form a distillate comprising the ester derivative followed by separation of the ester derivative from the distillate. Generally, the eluting liquid will also comprise water.
  • Suitable alcohols that may be used include in particular lower aliphatic alcohols having 1 to 5 carbon atoms such as methanol, ethanol and propanol. However aromatic alcohols may be used as well. Additionally, the alcohol may be added under the form of a precursor of the alcohol. Such a precursor should however form an alcohol under the conditions used to cause the esterification. Suitable precursors of the alcohol may include compounds such as ketals that readily form a corresponding alcohol under the acidic conditions existing in the eluting liquid or mixture thereof with the adsorbent particles. The acid used with the eluting fluid is preferably an inorganic acid but the use of organic acids is not excluded. Also, the acid is preferably a strong acid such as for example sulphuric acid, hydrochloric acid, phosphoric acid or nitric acid. The amount and nature of the acid used is typically such that a pH of less than 4, preferably not more than 3 and more preferably not more than 2 is attained in the mixture of eluting liquid and adsorbent particles.
  • Depending on the amount of water present in the distillate the ester derivative may separate out as a separate phase, typically the lower phase, from the distillate. Thus the ester derivative can be easily separated from the distillate and the remainder of the distillate can be re-introduced into the mixture being distilled. Such a circulating regeneration process thus allows a convenient regeneration of the adsorbent particles with a minimal amount of eluting fluid being needed. The received ester can be further purified by distilllation and is then converted to the fluorinated acid salt by saponification typically with ammonia. The eluated purified fluorinated carboxylic acid salt will typically have a purity sufficient to allow use of the compound in emulsion polymerization of fluorinated monomers. The adsorbent particles can be regenerated several times before their efficiency drops below an uneconomical level at which point the adsorbent particles need to be disposed of.
  • Following their recovery, the fluorinated carboxylic acids can be purified to the desired high purity enabling re-use of the fluorinated carboxylic acid in an aqueous emulsion polymerization. A suitable purification method is disclosed in U.S. Pat. No. 5,312,935. Herein the liberated and dewatered carboxylic acids are treated with oxidants like dichromates, peroxodisulfates or permanganates at a temperature of about 60° C. to the boiling point of the mixture. The pure product is then isolated by crystallization e.g. at low temperature or preferably by distillation if desired under reduced pressure. Alternatively, the method of WO 2004/031141 may be used.
  • EXAMPLES
  • Test Method:
  • Content of Fluorinated Carboxylic Acid
  • The amount of fluorinated carboxylic acid in aqueous solution was determined by conversion of the fluorinated emulsifier into the methyl ester followed by an analysis with gas chromatography (head space) using methyl ester of perfluorodecanoic acid as an internal standard. The detection limit was about 10 ppm.
  • Particle Size
  • The latex particle size determination was conducted by means of dynamic light scattering with a Malvern Zetazizer 1000 HAS in accordance to ISO/DIS 13321. Prior to the measurements, the polymer latexes as yielded from the polymerizations were diluted with 0.001 mol/L KCl-solution, the measurement temperature was 25° C. in all cases. The reported average is the Z-average particle diameter.
      • SSG: Standard specific gravity was measured according ASTM 4894-04
      • Solid Content: Determination of solid content was done by subjecting the latex sample to a temperature up to 250° C. for 30 min.
  • Polymerization of Fluorinated Monomers (Fluoroolefin) Using a Fluorinated Carboxylic Acid
  • The polymerization experiments were performed in a 40 l kettle equipped with an impeller agitator and a baffle. The kettle was charged with 30 l of deionized water and set to 35° C.; the kettle was evacuated repeatedly to remove oxygen; Agitation speed was set to 165 rpm. The oxygen free kettle was charged with 70 mmol fluorinated emulsifier (unless specified differently) as listed in table 3 and the following materials were added: 0.5 ml of a solution containing 40 mg of copper sulphate penta hydrate and 1 mg of conc. sulphuric acid; 15 g of a 25 w-% of aqueous ammonia solution and 5.6 g of CF3CF2CF2—O—CF(CF3)—CF2—O—CF═CF2 (PPVE-2). Finally the reactor was pressurized with tetrafluoroethylene (TFE) to 0.2 MPa and 47 g of hexafluoropropylene (HFP) were added. The kettle was then set to 1.5 MPa using TFE and 100 ml of an aqueous initiator solution containing 140 mg of sodium disulfite followed by 100 ml of a solution containing 340 mg of ammonium peroxodisulfate was pumped into the reactor. The beginning of the polymerization is indicated by a pressure drop. During polymerization the pressure was maintained at 1.5 MPa by feeding TFE continuously. After 3.2 kg of TFE had been added, the monomer valve was closed and the pressure was released. The characteristics of the obtained polymer latices are summarized in table 3.
  • 1000 ml of this polymer dispersion were coagulated by adding 20 ml hydrochloric acid under agitation. The coagulated material was agglomerated with gasoline and washed repeatedly. The agglomerated polymer was dried overnight at 200° C. in a vacuum oven; test data are given in table 3.
    TABLE 1
    Emulsifiers used:
    C7F15COONH4 Comparative
    example C-1
    Figure US20070025902A1-20070201-C00001
    Comparative example C-2
    Figure US20070025902A1-20070201-C00002
    Comparative example C-3
    CF3—O—(CF2)3—O—CF2—COONH4 Compound 1
    CF3—OCF2—O—CF2—COONH4 Compound 2
    CF3—OCF2—OCF2—OCF2—COONH4 Compound 3
    CF3—(OCF2)3—OCF2—COONH4 Compound 4
    C3F7—O—CF2—COONH4 Compound 5
    CF3—O—CF2—CF2—COONH4 Compound 6
    C2F5—O—CF2—CF2—COONH4 Compound 7
    C3F7—O—CF2—CF2—COONH4 Compound 8
    C4F9—O—CF2—CF2—COONH4 Compound 9
    C2F5—O—CF2—CF2—O—CF2—COONH4 Compound 10
    CF3—O—CF2—CF2—CF2—O—CHF—CF2—COONH4 Compound 11
    CF3—O—CF2—CF2—CF2—O—CHF—COONH4 Compound 12
    C3F7—O—CFH—CF2COONH4 Compound 13
    CF3—CFH—O—(CF2)5—COONH4 Compound 14
    CF3—CFH—O—(CF2)3—COONH4 Compound 15
    C3F7—O—CFH—CF2—O—CH2—COONH4 Compound 16
    C3F7—O—CFH—COONH4 Compound 17
  • Preparation of compound 1: CF3OCF2CF2CF2OCF2COONH4
  • Oxidation of perfluorinated vinyl ethers with oxygen in the presence of SbF5 was carried out as described in U.S. Pat. No. 4,987,254. The initially formed acid fluorides were esterified with methanol and purified by distillation. The distilled esters were converted to the corresponding ammonium salts by saponification with aqueous ammonia. A dry flask equipped with a magnetic stirrer bar, thermometer, dry ice reflux condenser, dropping funnel, and gas inlet tube was charged with 5 g of graphite. The flask was flushed with nitrogen and 332 g of CF3OCF2CF2CF2OCF═CF2 were added at room temperature. 2.6 g of SbF5 was added via the dropping funnel and oxygen was charged to the flask at ambient pressure. An exothermic reaction indicated the oxidation. Total reaction time was 14 h. After the first hour 2.6 g and after 7 hours 3.5 g of SbF5 were added. Esterification was achieved by slow addition of 50 g of methanol to the reaction mixture. The resulting ester was isolated from the batch by flash distillation after addition of 300 g water and 50 g methanol. The distillate formed two phases. The lower phase was separated and the upper phase retuned to the flask. 310 g of lower phase were collected. GC analysis showed a content of 52% of CF3OCF2CF2CF2OCF2COOCH3. Purification via fractionated distillation resulted in 144 g pure ester with a boiling point of 51° C. at 52 mbar. CF3OCF2CF2COOCH3 was isolated as by product. Saponification of the ester with aqueous ammonia at 60-80° C. and removal of methanol by distillation resulted in an aqueous solution of CF3OCF2CF2CF2OCF2COONH4. All structures were confirmed by F-NMR spectra.
  • Preparation of compound 5: CF3CF2CF2OCF2COONH4
  • Using the procedures described in U.S. Pat. No. 4,987,254, CF3CF2CF2OCF═CF2 was converted to CF3CF2CF2OCF2COOCH3 (bp 102-104° C.). Saponification with aqueous ammonia and removal of methanol by distillation resulted in an aqueous solution of CF3CF2CF2OCF2COONH4. Structures were confirmed by F-NMR spectra.
  • Preparation of compound 17: CF3CF2CF2OCHFCOONH4
  • A 2 liter glass flask equipped with a mechanical stirrer, thermometer and reflux condenser (−80° C.) is used. Heating of the flask is provided by an electric heating mantle. The conversion is carried out as a one pot reaction. 275 g perfluoropropyl vinyl ether (PPVE), 280 g KOH, 602 g water, 151 g t-butanol, and 10 g methyl trioctyl ammonium chloride are placed in the flask. The three phase mixture is subjected to vigorous stirring. After initial heating a moderate exothermic reaction occours. Mixing is continued for nine hours. During this time the internal temperature adjusts to 27-33° C. Mixing is stopped when the exothermic reaction ceases. The reaction mixture forms two layers. The low temperature reflux condenser is replaced by a standard reflux condenser. Sulfuric acid (392 g) is slowly added without external cooling. The batch is heated to reflux. Unreacted PPVE is vented. At about 80° C. internal temperature gas begins to evolve. Heating is continued until the gas evolution has ceased. At this time the internal temperature reaches 101° C. The batch is cooled to RT and the reflux condenser is replaced by a distillation device. No column is used. 110 g methanol is added to the batch and distillation is started.
  • The condensed vapors form two layers. The lower layer is separated and the upper layer is returned to the flask. Distillation is stopped when no more lower phase is formed. In total, 234 g of lower phase are collected. Fractionation of the lower phase yields 167 g of C3F7OCHFCOOCH3 with a boiling point of 120-122° C. at ambient pressure. Calculated yield: 59% based on total PPVE used; 70% based on converted PPVE. The ester is converted to the ammonium salt by reaction with aqueous ammonia. Methanol is removed by fractionated distillation. The resulting aqueous solution is used as an emulsifier in the polymerization of fluorinated olefins.
  • Preparation of compound 12: CF3OCF2CF2CF2OCHFCOONH4
  • A glass flask equipped with a reflux condenser, thermometer, and magnetic stirrer was used. Perfluoromethoxy propyl vinyl ether (498 g), t-butanol (149 g), water (1007 g), potassium hydroxide (280 g), and methyl trioctyl ammonium chloride (10 g) were added to the flask. The resulting two phase mixture was heated to reflux for 16 hours under vigorous stirring. The mixture was cooled to room temperature and sulphuric acid (588 g) was added. The two phase mixture was heated again under vigorous stirring. At about 70° C. gas began to evolve. Heating was continued until the gas evolution ceased. The reflux condenser was replaced by a distillation device which allowed the separation of a lower phase while returning the upper phase to the flask. Methanol (150 g) was added and the mixture was heated for distillation. Distillation was carried out at ambient pressure without any intent for rectification. The condensed vapors separated into two phases. The lower phase was collected and the upper phase was returned to the flask. Distillation was continued until no more lower phase separated from the condensate. The combined crude ester (493 g) was purified by fractionated distillation, resulting in 401 g CF3O(CF2)3OCHFCOOCH3 with a boiling point of 51 to 52° C./ 22 mbar. This corresponds to a yield of 78%, based on vinyl ether used.
  • The ester was converted to the ammonium salt by heating with aqueous ammonia and removal of methanol by fractionated distillation.
  • Alternatively, the previous reaction was repeated but 36 g of an aqueous solution containing 11 g of CF3O(CF2)3OCHFCOONH4 was used as phase transfer catalyst instead of methyl trioctyl ammonium chloride. The mixture was slowly heated to 70° C. internal temperature. Total reaction time was 26 hours. Work up was carried out as described above. 438 g of distilled CF3O(CF2)3OCHFCOOCH3 was received. This corresponds to a yield of 83% (calculation includes the amount of phase transfer catalyst). The conversion to the ammonium salt was carried out as above.
  • Preparation of compound 13: C3F7OCHFCF2COONH4 a. Preparation of CF3CF2CF2OCHFCF2CH2OH
  • In a 2 liter glass flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel were placed 1008 g methanol, 266 g perfluoropropyl vinyl ether, and 9.2 g of Rongalit® (sodium hydroxymethyl sulfinate). The reaction mixture was heated to reflux, resulting in an internal temperature of 29° C. 7.1 g t-butyl hydroperoxide (70% in water) is added in aliquots during a 9 h time frame. The internal temperature reached 52° C. at the end. The reaction mixture showed a single liquid phase and some solids. The liquid was analyzed by GC and indicated a content of 223 g of C3F7OCHFCF2CH2OH which corresponded to a yield of 75%.
  • Distillation of the reaction mixture resulted in 171 g of product (bp 54° C./23 mbar) corresponding to an isolated yield of 57%.
  • b. Preparation of C3F7OCHFCF2COONH4
  • A 2 liter glass flask equipped with a thermometer, reflux condenser, dropping funnel and stirrer was used. 674 g water, 136 g KMnO4, and 38 g NaOH are placed in the flask. 169 g C3F7OCHFCF2CH2OH were added to the well stirred mixture via the dropping funnel. The temperature is held below 50° C. Residual permanganate was destroyed by addition of a small amount of methanol. The resulting slurry was filtered to remove the MnO2. After washing the filter cake with water, the combined filtrate was transferred to a distillation apparatus and acidified with 65 g of sulfuric acid. 100 g methanol was added and a flash distillation was started. The distillate formed two layers. The lower layer was separated and the upper layer returned to the distillation pot. In total 182 g lower layer were collected. Fractionation of the crude ester resulted in 137 g of C3F7OCHFCF2COOCH3 with a boiling point of 55-56° C./52 mbar. This corresponds to a yield of 77%.
  • The ester was converted to the ammonium salt by saponification with aqueous ammonia and subsequent removal of methanol by distillation.
  • Preparation of compound 11: CF3O(CF2)3OCHFCF2COONH4 a. Preparation of CF3O(CF2)3OCHFCF2CH2OH
  • Using equipment similar to the described above, 255 g of perfluoromethoxypropyl vinyl ether and 730 g methanol were converted with Rongalit and t-butylhydroperoxide as radical source. Reaction temperature started at 47° C. and reached 64° C. at the end. Work up by distillation yielded 166 g of pure CF3O(CF2)3OCHFCF2CH2OH with a boiling point of 60-61° C./20 mbar. This corresponds to a yield of 59%.
  • b. Preparation of CF3O(CF2)3OCHFCF2COONH4
  • A 2 liter glass flask equipped with a thermometer, reflux condenser, dropping funnel and stirrer was used. 159 g of CF3O(CF2)3OCHFCF2CH2OH, 520 g water, and 100 g sulfuric acid were added to the flask. 190 g KMnO4 were added manually to the liquid over a period of 2 hours while stirring. The reaction temperature increased to 95° C. over time. After a post reaction time of two hours, an aqueous solution of sodium bisulfite was added until a clear solution was formed. 100 g of methanol and in total 400 g of 50% aqueous sulphuric acid were added. Flash distillation of the reaction mixture resulted in a two phase distillate. Fractionation of the lower phase (120 g) gave 85.5 g of CF3O(CF2)3OCHFCF2COOCH3 (bp 34-35° C./6 mbar; yield 50%).
  • The ester was converted to the ammonium salt by saponification with aqueous ammonia and subsequent removal of methanol by distillation.
  • Preparation of Compound 6
  • CH3—O—CF2—CF2—COOCH3 was fluorinated as described in WO 01/46116; the acid fluoride CF3—O—CF2—CF2—COF was then converted into the methylester. The distilled ester was converted into the ammonia-salt as described above.
  • Preparation of compound 14: CF3—CFH—O—(CF2)5COONH4
  • A sample of diacid fluoride, FCOCF(CF3)—O—(CF2)5COF (500 g, 1.1 mol) prepared from the hexafluoropropylene oxide (HFPO) coupling of perfluoroadipoyl fluoride as described in U.S. Pub. No. 2004/0116742 and was added over 2 hours to a stirred slurry of sodium carbonate (500 g, 4.7 mol) in 500 g of diglyme at 85° C. to make the disalt. The reaction liberated CO2 gas. Distilled water (25 g, 1.4 mol) was added at 85° C. The mixture was heated up to 168° C. with CO2 off-gassing and held for 30 minutes. Reaction was cooled down and sulphuric acid (350 g, 3.6 mol) in 1100 g of water was added to make the reaction mixture acidic. Bottom phase was washed with 400 g of 50% sulfuric acid and vacuum distilled to give CF3—CFH—O—(CF2)5COOH 426 g, 1.0 mol for a 95% yield having a boiling point of 132-135° C./15 mm. This was followed by the addition of 46 g NaOH in 63 g of water. Dried salts in vacuum oven at 112° C./15 mm Hg to give 386 g of slight yellow sticky solids. To the salt was added sulphuric acid and the lower fluorochemical phase was vacuum distilled. The previous process was repeated two more times to yield a colorless acid. The surfactant CF3—CFH—O—(CF2)5COONH4 having a melting point of 159-165° C. was made quantitatively from the reaction of 200 g of acid reacted with excess ammonium hydroxide and dried.
  • Preparation of Compound 15: CF3—CFH—O(CF2)3COONH4
  • A sample of diacid fluoride, FCOCF(CF3)—O—(CF2)3COF (503 g, 1.4 mol) prepared from the HFPO coupling of perfluorosuccinyl fluoride as described in U.S. Pub. No. 2004/0116742 and was added over 2 hours to a stirred slurry of sodium carbonate (387 g, 3.7 mol) in 650 g of diglyme at 78° C. to make the disalt. The reaction liberated CO2 gas. Distilled water (35 g, 1.9 mol) was added at 85° C. The mixture was heated up to 165° C. with CO2 off-gassing and held for 30 minutes. Reaction was cooled down and sulphuric acid (250 g, 2.6 mol) in 1250 g of water was added to make the reaction mixture acidic. To the bottom phase was added 60 g NaOH in 60 g of water. Dried the salt in vacuum oven at 112° C./15 mm and recovered 450 g. To the salt was added 300 g of 50% sulphuric acid and the lower fluorochemical phase was washed once with 200 g of 50% sulphuric acid. Vacuum distillation gave CF3—CFH—O—(CF2)3COOH (400 g, 1.3 mol) for a 95% yield having a boiling point of 111° C./15 mm Hg. The acid was treated with caustic followed by sulphuric acid and vacuum distilled. This was repeated a second time to yield a colorless acid. The surfactant CF3—CFH—O—(CF2)3COONH4 having a melting point of 64-68° C. was made quantitatively from the reaction of 208 g of acid reacted with excess ammonium hydroxide and dried.
  • Preparation of compound C-3
  • Conversion of CF3CF2CF2OCF(CF3)CF2OCF═CF2 to CF3CF2CF2OCF(CF3)CF2OCF2COOCH3 (bp 91-92° C. at 133 mbar) was carried described in U.S. Pat. No. 4,987,254. The ester was reacted with aqueous ammonia and methanol was removed by distillation resulting in CF3CF2CF2OCF(CF3)CF2OCF2COONH4. All structures were confirmed by F-NMR spectra. Due to an isomer content in the vinyl ether, an isomer with the structure CF3CF2CF2OCF2CF(CF3)OCF2COOX (X═CH3, NH4) was found.
  • Preparation of compound 16: C3F7—O—C2HF3—O—CH2—COONH4
  • A mixture of 320 ml Tetrahydrofurane, 40 g Hydroxy acetic methylester and 188 g PPVE is cooled to 0° C., 27 g KOH-powder are added in small portions—during the addition of KOH, the reaction mixture heats up to 60° C. After the addition of KOH, the whole reaction mixture is agitated for 6 h at 25° C. The precipitated salt is separated by filtration, dissolved in 300 ml water and then treated with 57 g H2SO4 (conc). The resulting mixture separates in two layers; the lower phase is C3F7—O—C2HF3—O—CH2—COOH, 86 g (56%). The distilled acid (bp. 125° C., 20 mbar) is neutralized with 25% aqueous ammonia solution to provide a 30% solution in water.
  • Compounds 2, 3, 4 were prepared from the corresponding carboxylic acids (purchased from Anles Ltd. St. Petersburg, Russia) by neutralizing with aqueous ammonia.
  • Compounds 7, 8, 10 were prepared from the corresponding carboxylic acid fluorides (˜COF) [purchased from Exfluor, Round Rock, Tex., USA]. The acid fluorides were converted by addition of methanol to the methylester. The distillated methylester were saponified with aqueous ammonia at 60-80° C. and methanol is removed by distillation.
  • Compound C-2 was prepared as described in U.S. Pat. No. 6,703,520 (column 7).
  • Determination of Bio-Accumulation
  • The perfluorinated and partially fluorinated carboxylates were evaluated for urinary clearance using a pharmacokinetic study in rats. The goal was to measure the total amount of parent compound eliminated via urinary output and estimate the rate of elimination. The study was approved by the IACUC (Institutional Animal Care and Use Committees) and was performed in 3M Company's AAALAC (Association for Assessment and Accreditation of Laboratory Animal Care)—accredited facility.
  • The study utilized male Sprague Dawley rats, 6 to 8 weeks of age, and approximately 200 to 250 g body weight at study onset. The test compounds of table 2 were administered at a dose of 73 micro Moles per kg body weight in rats (N=3 animals per tested compound). All test compounds were prepared in sterile deionized water and given to rats via oral gavage. After test compounds administration, the rats were housed individually in metabolism cages for urine collection: 0 to 6 hours, 6 to 24 hours, 24 to 48 hours and 72 to 96 hours. Animals were observed throughout the study for clinical signs of toxicity. Gross necropsy was performed at the termination of each study (96 hours post-dose) with sera and liver samples being retained from each animal.
  • The concentration of the parent compound or metabolites thereof were quantitatively measured via fluorine NMR on each urine sample for each animal at each time point based on internally added standards.
  • The bioaccumulation data obtained in accordance with the above test are reported in table 2 below.
    TABLE 2
    % Recovery Compound-related
    T½ (h) (96 h) Effects
    C-1 ˜550   6 Hepatomegaly
    C-2 29 40 Hepatomegaly
    C-3 95  5 Hepatomegaly
    Compound 1 10 73
    Compound 2 12 96
    Compound 3 12 100 
    Compound 4 15 50
    Compound 5 11 97
    Compound 6 11 100 
    Compound 7 10 100 
    Compound 8 12 82
    Compound 9 31 42 Hepatomegaly
    Compound 10 10 99
    Compound 11 12 84
    Compound 12 11 95
    Compound 13 11 94
    Compound 14 24 32 Hepatomegaly
    Compound 15  8 95
    Compound 16  13*  65*

    *No parent compound observed in the urine. T½ and % recovery are based on elimination of the major metabolite —C3F7—O—CHFCOO. T1/2 is the renal half-life and is the time required for the amount of a particular substance in a biological system to be reduced to one half of its value by biological processes when the rate of removal is
    # approximately exponential. In these examples the value of T1/2 is calculated by exponential least squares curve fitting (y = AeBx and T1/2 = 0.693/B) where y represents the concentration of analyte in urine and x represents time in hours.
  • TABLE 3
    2
    C-1 C-2 C-3 1 (140 mmol) 3 4 5 6
    Polymerization 101 77 87 74 109 69 82 73 84
    time (min)
    Average Particle 111 118 113 110 129 115 109 122 122
    Size (nm)
    SSG 2.166 2.165 2.149 2.169 2.157 2.165 2.163 2.169 2.175
    (g/cm3)
    Solid content 9.9 10.0 10.3 10.3 9.7 10.1 10.2 10.0 7.1
    (w-%)
    7 14
    (140 mmol) 8 9 10 11 12 13 (140 mmol) 15
    Polymerization 73 79 72 72 82 82 83 75 78
    time (min)
    Average Particle 129 115 113 102 126 108 128 127 105
    Size (nm)
    SSG 2.159 2.167 2.165 2.166 2.168 2.167 2.164 2.151 2.154
    (g/cm3)
    Solid content 10.1 10.0 10.2 10.1 10.2 10.3 10.2 8.1 10.
    (w-%)
  • Recovery of Fluorinated Ether Carboxylic Acids from Adsorbents
  • 300 ml of Amberlite IRA 402 OH a strong basic anion exchanger from Rohm & Haas was charged with CF3O(CF2)3OCF2COONH4 until break-through. The resin was transferred into a column and washed with 3 1 of deionized water.
  • 700 ml of a mixture of 60:20:20 wt-% of methanol:water: sulphuric acid (conc.) (herein called regeneration solution) was circulated for 6 hours through the column with a flow rate of about 1.4 l/h. The regeneration solution was pumped from the top of a feeding tank through the column and back into the feeding tank (flow direction through the column from top to bottom). The elution was done at room temperature. During the recovery step phase separation occurred in the tank due to the formation of the corresponding ester (CF3O(CF2)3OCF2COOCH3). The lower phase, essentially consisting of the ester was separated.
  • The resin was then washed with 1.5 l of methanol/water (90:10 wt-%) and 800 ml of deionized water (both with a flow rate of 300 ml/h). The washing solutions and the upper phase of the tank were allowed to stand for a period of 16 hours to achieve additional phase separation. The lower phase was separated and added to the ester phase.
  • The upper phase, mainly containing methanol, water, sulphuric acid and residual ester, was distillated under atmospheric pressure. The purified methanol contained residual amount of ester and was used for the next regeneration process. The overall recovery efficiency calculated on ester was about 88%. The regenerated ion-exchange resin could be re-used several times.
  • Recycling of Fluorinated Ether Carboxylic Acids
  • 70 g of CF3O(CF2)3OCF2COOCH3, 50 g methanol, 30 g water and 7 g of sulphuric acid were flash distillated at atmospheric pressure. The distillate formed two phases and the upper phase was returned to the flask. The lower phase, mainly consisting of the ester (CF3O(CF2)3OCF2COOCH3) was separated and purified in a further step via fractionated distillation. 53 g of pure ester were collected at a boiling point of about 50° C. at 50 mbar. The ester was saponified with aqueous ammonia at 60-80° C. and methanol was removed by distillation. The resulting aqueous solution of CF3O(CF2)3OCF2COONH4 was used as an emulsifier for tetrafluoroethylene polymerization to show “polymerization grade” of the product after the recycling process. No deviation between virgin and recycled material was observed during polymerization process.

Claims (24)

1. A process comprising recovery of fluorinated carboxylic acid or derivative thereof from adsorbent particles on which fluorinated carboxylic acid or a salt thereof is adsorbed, by contacting said adsorbent particles with a liquid composition capable of removing at least part of said fluorinated carboxylic acid or salt thereof from said adsorbent particles, wherein said fluorinated carboxylic acid or salt thereof is selected from the group consisting of fluorinated carboxylic acids or salts thereof that correspond to the general formula:

[Rf—O-L-COO]iXi+
wherein L represents a linear partially or fully fluorinated alkylene group or an aliphatic hydrocarbon group, Rf represents a linear partially or fully fluorinated aliphatic group or a linear partially or fully fluorinated aliphatic group interrupted with one or more oxygen atoms, Xi+ represents a cation having the valence i and i is 1, 2 or 3.
2. A process according to claim 1 wherein said liquid composition is capable of dissolving said fluorinated carboxylic acid or a salt thereof.
3. A process according to claim 1 wherein said liquid composition is capable of converting said fluorinated carboxylic acid or salt thereof into a corresponding ester and wherein said ester is removed by distillation from a mixture of adsorbent particles and said liquid composition.
4. A process according to claim 1 wherein said adsorbent particles are selected from the group consisting of anion exchange resin, active carbon, alumina, celites, clay and zeolites.
5. A process according to claim 3 wherein said liquid composition comprises an alcohol.
6. A process according to claim 5 wherein liquid composition further comprises an acid.
7. A process according to claim 2 wherein said liquid composition comprises an alkaline solution.
8. A process according to claim 7 wherein the liquid composition comprises an organic solvent and a base selected from the group consisting of ammonia, alkali hydroxides and mixtures thereof.
9. A process according to claim 1 wherein said adsorbent particles comprise an anion exchange resin and wherein said liquid composition comprises an ammonium salt dissolved in an organic solvent.
10. A process according to claim 1 wherein the anion of said fluorinated carboxylic acids or salts thereof have a molecular weight of not more than 1000 g/mol.
11. A process according to claim 1 wherein the anion of said fluorinated carboxylic acids or salts thereof have a molecular weight of not more than 500 g/mol.
12. A process according to claim 1 wherein the fluorinated carboxylic acid or salt thereof when administered to rat shows a renal recovery rate of at least 50% of the administered amount, 96 hours after administration and wherein the renal half-life (T1/2) is not more than 30 hours.
13. A process according to claim 1 wherein the fluorinated carboxylic acid or salts are selected from fluorinated carboxylic acid or salts of which any fluorinated aliphatic portion has not more than 3 carbon atoms.
14. A process according to claim 1 wherein L in said formula is selected from the group consisting of linear perfluorinated alkylene groups having 1 to 6 carbon atoms, linear partially fluorinated alkylene groups having 1 to 6 carbon atoms having not more than 2 hydrogen atoms and aliphatic hydrocarbon groups having 1 to 6 carbon atoms.
15. A process according to claim 1 wherein Rf is selected from the group consisting of linear perfluorinated aliphatic groups having 1 to 6 carbon atoms; linear perfluorinated aliphatic groups interrupted with one or more oxygen atoms of which alkylene groups between oxygen atoms have not more than 6 carbon atoms and wherein the terminal alkyl group has not more than 6 carbon atoms; linear partially fluorinated aliphatic groups having 1 to 6 carbon atoms and not more than 2 hydrogen atoms and linear partially fluorinated aliphatic groups interrupted with one or more oxygen atoms and which have not more than 2 hydrogen atoms.
16. A process according to claim 1 wherein L is selected from the group consisting of
—(CF2)g— wherein g is 1, 2, 3, 4, 5 or 6; —CFH—(CF2)h— wherein h is 0, 1, 2, 3, 4 or 5;
—CF2—CFH—(CF2)d— wherein d is 0, 1, 2, 3 or 4; —CH2—(CF2)h— wherein h is 1, 2, 3 or 4;
and —(CH2)c— wherein c is 1, 2, 3 or 4.
17. A process according to claim 1 wherein Rf corresponds to the following formula:

Rf 1—[ORf 2]p—[ORf 3]q—  (II)
wherein Rf 1 is a perfluorinated linear aliphatic group of 1 to 6 carbon atoms, Rf 2 and Rf 3 each independently represents a linear perfluorinated alkylene of 1, 2, 3 or 4 carbon atoms and p and q each independently represent a value of 0 to 4 and wherein the sum of p and q is at least 1.
18. A process according to claim 1 wherein Rf corresponds to the following formula:

R7 f—(O)t—CFH—CF2—  (III)
wherein t is 0 or 1 and R7 f represents a linear partially or fully fluorinated aliphatic group optionally interrupted with one or more oxygen atoms.
19. A process according to claim 1 wherein Rf corresponds to the formula:

Rf 8—(OCF2)a—  (IV)
wherein a is an integer of 1 to 6 and Rf 8 is a linear partially fluorinated aliphatic group or a linear fully fluorinated aliphatic group having 1, 2, 3 or 4 carbon atoms.
20. A process according to claim 1 wherein Rf corresponds to the formula:

Rf 9—O—(CF2)b—  (V)
wherein b is an integer of 1 to 6, preferably 1, 2, 3 or 4 and Rf 9 is a linear partially fluorinated aliphatic group or a linear fully fluorinated aliphatic group having 1, 2, 3 or 4 carbon atoms.
21. A process according to claim 1 wherein the fluorinated carboxylic acid corresponds to the following formula:

[Rf a—(O)t—CHF—(CF2)n—COO]iXi+  (VI)
wherein Rf a represents a linear partially or fully fluorinated aliphatic group optionally interrupted with one or more oxygen atoms, t is 0 or 1 and n is 0 or 1, Xi+ represents a cation having a valence i and i is 1, 2 or 3, with the proviso that when t is 0, the Rf a contains at least one ether oxygen atom.
22. A process according to claim 1 wherein the fluorinated carboxylic acid corresponds to the following formula:

Rf b—(O)t—CFH—CF2—O—R-G   (VII)
wherein Rf b represents a linear partially or fully fluorinated aliphatic group optionally interrupted with one or more oxygen atoms, R is an aliphatic hydrocarbon group, G represents a carboxylic acid or salt thereof, t is 0 or 1.
23. A process according to claim 1 wherein the fluorinated carboxylic acid corresponds to one of the following formulas:

Rf c—(OCF2)u—O—(CF2)v-AC   (VIII)
wherein u is an integer of 1 to 6, v is an integer of 1 to 6, Rf c represents a linear perfluorinated aliphatic group of 1, 2, 3 or 4 carbon atoms and AC represents a carboxylic acid group or salt thereof, and

Rf c—O—(CF2)y—O-L1-AC   (IX)
wherein y has a value of 1, 2, 3, 4, 5 or 6, L1 represents a linear perfluorinated alkylene of 1, 2, 3, 4, 5 or 6 carbon atoms or a partially fluorinated alkylene having 1 to 6 carbon atoms and 1 or 2 hydrogen atoms, Rf c is as defined in above formula (VIII) and AC represents a carboxylic acid group or salt thereof.
24. A process according to claim 1 wherein the fluorinated carboxylic acid or salt thereof is selected from the group consisting of
C3F7—O—CHF—COOH
CF3—O—CF2CF2—CF2—O—CHF—COOH
CF3CF2CF2—O—CF2CF2—CF2—O—CHF—COOH
CF3—O—CF2—CF2—O—CHF—COOH
CF3—O—CF2—O—CF2—CF2—O—CHF—COOH
CF3—(O—CF2)2—O—CF2—CF2—O—CHF—COOH
CF3—(O—CF2)3—O—CF2—CF2—O—CHF—COOH
CF3—O—CHF—CF2—COOH
CF3—O—CF2—CF2—O—CHF—CF2—COOH
CF3—CF2—O—CHF—CF2—COOH
CF3—O—CF2—CF2—CF2—O—CHF—CF2—COOH
CF3—O—CF2—O—CF2—CF2—O—CHF—CF2—COOH
CF3—(O—CF2)2—O—CF2—CF2—O—CHF—CF2—COOH
CF3—(O—CF2)3—O—CF2—CF2—O—CHF—CF2—COOH
CF3—O—CF2—CHF—COOH
C3F7—O—CF2—CHF—COOH
CF3—O—CF2—CF2—CF2—O—CF2—CHF—COOH
CF3—O—CF2—O—CF2—CF2—O—CF2—CHF—COOH
CF3—(O—CF2)2—O—CF2—CF2—O—CF2—CHF—COOH
CF3—(O—CF2)3—O—CF2—CF2—O—CF2—CHF—COOH
CF3—O—CF2—CHF—CF2—COOH
C2F5—O—CF2—CHF—CF2—COOH
C3F7—O—CF2—CHF—CF2—COOH
CF3—O—CF2—CF2—CF2—O—CF2—CHF—CF2—COOH
CF3—O—CF2—O—CF2—CF2—O—CF2—CHF—CF2—COOH
CF3—(O—CF2)2—O—CF2—CF2—O—CF2—CHF—CF2—COOH
CF3—(O—CF2)3—O—CF2—CF2—O—CF2—CHF—CF2—COOH
CF3—O—CHF—CF2—O—CH2—COOH
CF3—O—CF2—CF2—CF2—O—CHF—CF2—O—CH2—COOH
C3F7—O—CHF—CF2—O—CH2—COOH
C3F7—O—CHF—CF2—O—CH2—CH2—COOH
C3F7—O—CF2—CF2—O—CHF—CF2—OCH2COOH
C3F7—O—CF2—CF2—CF2—O—CHF—CF2—OCH2COOH
C3F7—O—CF2—CHF—CF2—OCH2COOH
CF3—CHF—CF2—O—CH2COOH
C3F7—CF2—CHF—CF2—OCH2—COOH
CF3—O—CF2—CF2—O—CH2—COOH
CF3—O—CF2—CF2—CF2—O—CF2—CF2—O—CH2—COOH
C3F7—O—CF2—CF2—O—CH2—COOH
C3F7—O—CF2—CF2—O—CH2—CH2—COOH
C3F7—O—CF2—CF2—O—CF2—CF2—OCH2COOH
C3F7—O—CF2—CF2—CF2—O—CF2—CF2—OCH2COOH
C3F7—O—CF2—CF2—CF2—OCH2COOH
C4F9—O—CH2—COOH
C4F9—O—CH2—CH2—COOH
C3F7—O—CH2COOH
C6F13—OCH2—COOH
CF3—O—CF2—CF2—COOH
C2F5—O—CF2—CF2—COOH
C3F7—O—CF2—CF2—COOH
C4F9—O—CF2—CF2—COOH
CF3—(O—CF2)3—O—CF2—COOH
CF3—(O—CF2)2—O—CF2—COOH
CF3—(O—CF2)1—O—CF2—COOH
CF3—(O—CF2—CF2)1—O—CF2—COOH
C2F5—(O—CF2—CF2)1—O—CF2—COOH
C2F5—(O—CF2—CF2)2—O—CF2—COOH
CF3—(O—CF2—CF2)2—O—CF2—COOH
C3F7—O—CF2—COOH
CF3—O—CF2—CF2—CF2—O—CF2—COOH
CF3CFH—O—(CF2)3—COOH
CF3CFH—O—(CF2)5—COOH
CF3—CF2—O—(CF2)3COOH
CF3—CF2—O—(CF2)5COOH
and salts of any of these fluorinated carboxylic acids.
US11/420,413 2005-07-15 2006-05-25 Recovery of fluorinated carboxylic acid from adsorbent particles Abandoned US20070025902A1 (en)

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GBGB0514398.7A GB0514398D0 (en) 2005-07-15 2005-07-15 Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
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GBGB0523853.0A GB0523853D0 (en) 2005-11-24 2005-11-24 Fluorinated surfactants for use in making a fluoropolymer
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US11/420,416 Active 2028-09-11 US7795332B2 (en) 2005-07-15 2006-05-25 Method of removing fluorinated carboxylic acid from aqueous liquid
US11/420,386 Active 2027-01-26 US7671112B2 (en) 2005-07-15 2006-05-25 Method of making fluoropolymer dispersion
US12/684,239 Active 2026-12-05 US8222322B2 (en) 2005-07-15 2010-01-08 Method of making fluoropolymer dispersion
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US20090281261A1 (en) * 2008-05-09 2009-11-12 E. I. Du Pont De Nemours And Company Abatement of Fluoroether Carboxylic Acids or Salts Employed in Fluoropolymer Resin Manufacture
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US20110160415A1 (en) * 2008-07-08 2011-06-30 Solvay Solexis S.P.A. Method for manufacturing fluoropolymers
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US8329813B2 (en) 2009-05-08 2012-12-11 E I Du Pont De Nemours And Company Thermal reduction of fluoroether carboxylic acids or salts from fluoropolymer dispersions
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WO2018167190A1 (en) 2017-03-17 2018-09-20 Solvay Specialty Polymers Italy S.P.A. Method for making fluoropolymers
WO2018181898A1 (en) 2017-03-31 2018-10-04 ダイキン工業株式会社 Production method for fluoropolymer, surfactant for polymerization, and use of surfactant
WO2018181904A1 (en) 2017-03-31 2018-10-04 ダイキン工業株式会社 Production method for fluoropolymer, surfactant for polymerization, and use of surfactant
US20190070599A1 (en) * 2016-03-04 2019-03-07 3M Innovative Properties Company Method for removing perfluorinated alkanoic acids
WO2019048394A1 (en) 2017-09-08 2019-03-14 Solvay Specialty Polymers Italy S.P.A. Method for making fluoropolymers
US10377843B2 (en) 2014-05-12 2019-08-13 Solvay Specialty Polymers Italy S.P.A. Method for the controlled polymerization of fluoromonomers
WO2019156175A1 (en) 2018-02-08 2019-08-15 ダイキン工業株式会社 Method for manufacturing fluoropolymer, surfactant for polymerization, use for surfactant, and composition
WO2019168183A1 (en) 2018-03-01 2019-09-06 ダイキン工業株式会社 Method for manufacturing fluoropolymer
WO2019172382A1 (en) 2018-03-07 2019-09-12 ダイキン工業株式会社 Method for producing fluoropolymer
WO2020104889A1 (en) 2018-11-20 2020-05-28 3M Innovative Properties Company Curable composition containing a polyether-modified polydimethyl siloxane
WO2020213691A1 (en) 2019-04-16 2020-10-22 ダイキン工業株式会社 Method for producing fluoropolymer powder
WO2020218618A1 (en) 2019-04-26 2020-10-29 ダイキン工業株式会社 Process for producing aqueous fluoropolymer dispersion
WO2020250129A1 (en) 2019-06-12 2020-12-17 3M Innovative Properties Company Process of taking a dental impression with a radiation-curable composition containing mercapto-functional polyorganosiloxanes and vqm resins
WO2021015291A1 (en) 2019-07-23 2021-01-28 ダイキン工業株式会社 Method for producing fluoropolymer, polytetrafluoroethylene composition, and polytetrafluoroethylene powder
WO2021045165A1 (en) 2019-09-05 2021-03-11 ダイキン工業株式会社 Method for producing perfluoroelastomer and composition
WO2021100835A1 (en) 2019-11-19 2021-05-27 ダイキン工業株式会社 Method for producing fluoropolymer
US11072671B2 (en) 2010-04-28 2021-07-27 3M Innovative Properties Company Process for producing PTFE and articles thereof
EP3945099A1 (en) 2020-07-30 2022-02-02 3M Innovative Properties Company Process for removal of fluoroorganic compounds from aqueous media
EP3945075A1 (en) 2020-07-30 2022-02-02 3M Innovative Properties Company Process for removal of fluoroorganic compounds from emulsions
EP3945074A1 (en) 2020-07-30 2022-02-02 3M Innovative Properties Company Process to reduce the concentration of fluoroorganic acidic compound in aqueous dispersions
WO2022107890A1 (en) 2020-11-19 2022-05-27 ダイキン工業株式会社 Method for manufacturing perfluoroelastomer aqueous dispersion, composition, crosslinkable composition, and crosslinked product
WO2022107891A1 (en) 2020-11-19 2022-05-27 ダイキン工業株式会社 Method for producing fluorine-containing elastomer aqueous dispersion, and composition
WO2022196804A1 (en) 2021-03-18 2022-09-22 ダイキン工業株式会社 Method for producing fluororesin, fluororesin, and aqueous dispersion liquid
WO2022244784A1 (en) 2021-05-19 2022-11-24 ダイキン工業株式会社 Method for producing fluoropolymer, method for producing polytetrafluoroethylene, and composition
WO2022248954A1 (en) 2021-05-26 2022-12-01 3M Innovative Properties Company Dental composition comprising an isorbide component
WO2022260139A1 (en) 2021-06-11 2022-12-15 ダイキン工業株式会社 Production method for aqueous fluorine-containing elastomer dispersion, composition, and aqueous dispersion
WO2023277139A1 (en) 2021-06-30 2023-01-05 ダイキン工業株式会社 Method for producing fluoropolymer composition, and fluoropolymer composition
WO2023277140A1 (en) 2021-06-30 2023-01-05 ダイキン工業株式会社 Method for producing high-purity fluoropolymer-containing composition, and high-purity fluoropolymer-containing composition
EP4219412A1 (en) 2022-01-27 2023-08-02 3M Innovative Properties Company Closed-loop technologies for purifying fluorine containing water streams
WO2023165912A1 (en) 2022-03-01 2023-09-07 Solvay Specialty Polymers Italy S.P.A. Method for making fluoropolymers containing ion exchange groups

Families Citing this family (184)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9187347B2 (en) * 2002-11-19 2015-11-17 Xogen Technologies Inc. Treatment of a waste stream through production and utilization of oxyhydrogen gas
US9296629B2 (en) 2002-11-19 2016-03-29 Xogen Technologies Inc. Treatment of a waste stream through production and utilization of oxyhydrogen gas
US7169933B2 (en) * 2003-11-14 2007-01-30 3M Innovative Properties Company N-sulfonylaminocarbonyl containing compounds
US7514484B2 (en) * 2005-06-06 2009-04-07 Asahi Glass Company, Limited Aqueous dispersion of polytetrafluoroethylene and process for its production
JP4956925B2 (en) * 2005-07-13 2012-06-20 旭硝子株式会社 Polytetrafluoroethylene aqueous dispersion and process for producing the same
GB2430437A (en) * 2005-09-27 2007-03-28 3M Innovative Properties Co Method of making a fluoropolymer
US7404907B2 (en) * 2005-12-19 2008-07-29 Kelydra Elizabeth Welcker Removal and recovery of ammonium perfluorooctanoate (APFO) from contaminated water
US7977438B2 (en) 2006-11-09 2011-07-12 E. I. Du Pont De Nemours And Company Aqueous polymerization of fluorinated monomers using polymerization agent comprising fluoropolyether acid or salt and siloxane surfactant
US7897682B2 (en) 2006-11-09 2011-03-01 E. I. Du Pont De Nemours And Company Aqueous polymerization of fluorinated monomers using polymerization agent comprising fluoropolyether acid or salt and hydrocarbon surfactant
US7932333B2 (en) 2006-11-09 2011-04-26 E.I. Du Pont De Nemours And Company Aqueous polymerization of fluorinated monomer using polymerization agent comprising high molecular weight fluoropolyether acid or salt and fluoropolyether acid or salt surfactant
WO2008109219A1 (en) * 2007-03-06 2008-09-12 3M Innovative Properties Company System and process for ultrasonically induced cavitation of fluorochemicals
US8025974B2 (en) * 2007-04-04 2011-09-27 Aculon, Inc. Inorganic substrates with hydrophobic surface layers
US20080264864A1 (en) * 2007-04-27 2008-10-30 3M Innovative Properties Company PROCESS FOR REMOVING FLUORINATED EMULSIFIER FROM FLUOROPOLMER DISPERSIONS USING AN ANION-EXCHANGE RESIN AND A pH-DEPENDENT SURFACTANT AND FLUOROPOLYMER DISPERSIONS CONTAINING A pH-DEPENDENT SURFACTANT
GB0709033D0 (en) * 2007-05-11 2007-06-20 3M Innovative Properties Co Melt-Processible fluoropolymers having long-chain branches, Methods of preparing them and uses thereof
JP2010528159A (en) * 2007-05-23 2010-08-19 スリーエム イノベイティブ プロパティズ カンパニー Aqueous composition of fluorinated surfactant and method of use
CN101679569A (en) * 2007-06-06 2010-03-24 3M创新有限公司 Fluorinated ether compositions and methods of using the same
GB0712191D0 (en) * 2007-06-25 2007-08-01 3M Innovative Properties Co Process for removing fluorinated compounds for an aqueous phase originating from the preparation of fluoropolymers
JP5257360B2 (en) * 2007-06-28 2013-08-07 ダイキン工業株式会社 Polytetrafluoroethylene aqueous dispersion and process for producing the same
WO2009014167A1 (en) * 2007-07-24 2009-01-29 Daikin Industries, Ltd. Novel compound, method for producing the same and method for producing fluoropolymer
GB0716421D0 (en) 2007-08-23 2007-10-03 3M Innovative Properties Co Method of preparing fluoropolymers by aqueous emulsion polymerization
JP5584123B2 (en) * 2007-09-14 2014-09-03 スリーエム イノベイティブ プロパティズ カンパニー Ultra low viscosity iodine-containing amorphous fluoropolymer
US8217126B2 (en) * 2007-11-09 2012-07-10 E I Du Pont De Nemours And Company Fluoroolefin monomers and copolymers thereof
WO2009085899A1 (en) * 2007-12-21 2009-07-09 3M Innovative Properties Company Methods for treating hydrocarbon-bearing formations with fluorinated anionic surfactant compositions
JP5881269B2 (en) * 2008-01-03 2016-03-09 ダイキン工業株式会社 Fluoroethercarboxylic acid and method for producing the same, surfactant, method for producing fluoropolymer using the same, and aqueous dispersion
GB0801194D0 (en) * 2008-01-23 2008-02-27 3M Innovative Properties Co Processing aid compositions comprising fluoropolymers having long-chain branches
CN102007150B (en) * 2008-02-29 2015-09-23 3M创新有限公司 There is the Perfluoroelastomer of low carbonyl endgroup ratios
US20090281241A1 (en) * 2008-05-09 2009-11-12 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Fluorinated Monomer Using a Mixture of Fluoropolyether Acids or Salts
EP2143738A1 (en) 2008-07-08 2010-01-13 Solvay Solexis S.p.A. Method for manufacturing fluoropolymers
US8633288B2 (en) * 2008-07-18 2014-01-21 3M Innovative Properties Company Fluorinated ether compounds and methods of using the same
CN102282191A (en) * 2008-11-25 2011-12-14 3M创新有限公司 Fluorinated ether urethanes and methods of using the same
CN102317403A (en) 2008-12-18 2012-01-11 3M创新有限公司 Method of contacting hydrocarbon-bearing formations with fluorinated ether compositions
US8436054B2 (en) * 2008-12-23 2013-05-07 E I Du Pont De Nemours And Company Fluorinated ionomer produced by aqueous polymerization using dispersed particulate of fluorinated ionomer produced in situ
US20100160552A1 (en) * 2008-12-23 2010-06-24 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Fluorinated Monomer Using Hydrogen Containing Branched Fluoroether Surfactant
CN102264774A (en) 2008-12-23 2011-11-30 杜邦公司 Fluorinated ionomer produced by aqueous polymerization using dispersed particulate of fluorinated ionomer
US8153738B2 (en) 2008-12-23 2012-04-10 E I Du Pont De Nemours And Company Fluoropolymer produced by aqueous polymerization using dispersed particulate of fluorinated ionomer
US8835547B2 (en) * 2008-12-23 2014-09-16 E I Du Pont De Nemours And Company Fluoropolymer particles having a nucleus of fluorinated ionomer
US8436053B2 (en) * 2008-12-23 2013-05-07 E.I. Du Pont De Nemours And Company Fluorinated ionomer produced by aqueous polymerization using dispersed particulate of fluorinated ionomer
US8058376B2 (en) 2008-12-23 2011-11-15 E. I. Du Pont De Nemours And Company Fluoropolymer produced by aqueous polymerization using dispersed particulate of fluorinated lonomer produced in situ
US8993679B2 (en) 2009-03-12 2015-03-31 Daikin Industries, Ltd. Method for producing aqueous dispersion of fluorine-containing seed polymer particles and aqueous coating composition and coated article thereof
WO2010113950A1 (en) 2009-03-30 2010-10-07 ダイキン工業株式会社 Polytetrafluoroethylene and method for producing same
MX2012000413A (en) 2009-07-09 2012-02-08 3M Innovative Prosperties Company Methods for treating carbonate hydrocarbon-bearing formations with fluorinated amphoteric compounds.
CN102482362B (en) 2009-08-28 2014-05-14 大金工业株式会社 Method for producing fluorine-containing polymer
CN102482363B (en) 2009-08-28 2014-01-01 大金工业株式会社 Method for producing fluorine-containing polymer
GB0918616D0 (en) * 2009-10-23 2009-12-09 3M Innovative Properties Co Method of preparing highly fluorinated carboxylic acids and their salts
WO2011097369A1 (en) * 2010-02-05 2011-08-11 Conocophillips Company Electrocoagulation for removal of dissolved organics from water
WO2011101342A1 (en) * 2010-02-18 2011-08-25 Lanxess Deutschland Gmbh Treatment of waste water containing fluorinated acids or the salts thereof
US9168408B2 (en) * 2010-03-25 2015-10-27 The Chemours Company Fc, Llc Surfactant composition from polyfluoroalkylsulfonamido alkyl amines
WO2011162971A2 (en) 2010-06-24 2011-12-29 3M Innovative Properties Company Polymerizable compositions free of organic emulsifier and polymers and methods of making thereof
US20120007267A1 (en) 2010-07-07 2012-01-12 Lifoam Industries Method of Producing Compostable or Biobased Foams
EP2409998B1 (en) 2010-07-23 2015-11-25 3M Innovative Properties Company High melting PTFE polymers suitable for melt-processing into shaped articles
US8962706B2 (en) 2010-09-10 2015-02-24 Lifoam Industries, Llc Process for enabling secondary expansion of expandable beads
WO2012064858A1 (en) 2010-11-09 2012-05-18 E. I. Du Pont De Nemours And Company Reducing the telogenic behavior of hydrocarbon-containing surfactants in aqueous dispersion fluoromonomer polymerization
CN106674392B (en) 2010-11-09 2019-10-18 科慕埃弗西有限公司 Nucleation in the aqueous polymerization reaction of fluorochemical monomer
JP6109073B2 (en) 2010-11-09 2017-04-05 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company Aqueous polymerization of fluoromonomers using hydrocarbon surfactants.
JP5866375B2 (en) 2010-12-17 2016-02-17 スリーエム イノベイティブ プロパティズ カンパニー Fluorine-containing polymers containing sulfinate-containing molecules
CN103261361B (en) 2010-12-20 2016-06-15 3M创新有限公司 For the method with fluoride amine oxide process carbonate hydrocarbon containing formation
BR112013015923A2 (en) 2010-12-21 2018-06-05 3M Innovative Properties Co method for treating hydrocarbon containing formations with fluorinated amine.
CN102558721B (en) 2010-12-31 2014-08-20 杜邦公司 Novel polytetrafluoroethylene aqueous dispersion
EP2663608A4 (en) 2011-01-13 2014-07-09 3M Innovative Properties Co Methods for treating siliciclastic hydrocarbon-bearing formations with fluorinated amine oxides
JP6382105B2 (en) 2011-08-04 2018-08-29 スリーエム イノベイティブ プロパティズ カンパニー Low equivalent weight polymer
EP2557109B1 (en) 2011-08-11 2019-01-23 3M Innovative Properties Company Method of bonding a fluoroelastomer compound to a metal substrate using low molecular weight functional hydrocarbons as bonding promoter
EP2788318A2 (en) 2011-12-06 2014-10-15 3M Innovative Properties Company Fluorinated oligomers having pendant functional groups
EP2791240B1 (en) 2011-12-16 2018-01-24 3M Innovative Properties Company Processing aid composition derived from a sulfinate-containing molecule
EP2620471B1 (en) 2012-01-27 2021-03-10 3M Innovative Properties Company Polytetrafluoroethene compound with microspheres and fibers
US9080070B2 (en) 2012-04-03 2015-07-14 Gem Gravure Co., Inc. Inkjet ink for printing on fluoropolymers
KR102120657B1 (en) 2012-11-05 2020-06-09 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Peroxide-curable fluoropolymer composition including solvent and method of using the same
JP6308949B2 (en) 2012-11-30 2018-04-11 ダイキン工業株式会社 Method for producing aqueous fluoropolymer dispersion
EP2927248B1 (en) 2012-11-30 2018-06-13 Daikin Industries, Ltd. Production method for polytetrafluoroethylene aqueous dispersion
CN104812780B (en) 2012-11-30 2021-10-22 大金工业株式会社 Aqueous polytetrafluoroethylene dispersion and polytetrafluoroethylene fine powder
US9260553B2 (en) 2012-12-04 2016-02-16 3M Innovative Properties Company Highly fluorinated polymers
EP2928931B1 (en) 2012-12-04 2017-03-01 3M Innovative Properties Company Partially fluorinated polymers
EP2931693B1 (en) 2012-12-14 2020-03-18 3M Innovative Properties Company Partially fluorinated compounds
WO2014099311A1 (en) 2012-12-19 2014-06-26 3M Innovative Properties Company Method of making fluoropolymers with a polyiodide, compositions and articles thereof
EP2935444B1 (en) 2012-12-20 2019-09-18 3M Innovative Properties Company Composite particles including a fluoropolymer, methods of making, and articles including the same
EP2767557B1 (en) 2013-02-14 2017-03-22 3M Innovative Properties Company Fluoropolymer compositions with microspheres
WO2014165998A1 (en) * 2013-04-10 2014-10-16 Xogen Technologies Inc. Treatment of a waste stream through production and utilization of oxyhydrogen gas
EP3004223B1 (en) * 2013-06-04 2021-03-17 Solvay Specialty Polymers Italy S.p.A. Process for manufacturing fluoropolymer composites
JP6571639B2 (en) 2013-06-14 2019-09-04 スリーエム イノベイティブ プロパティズ カンパニー Fluoropolymer containing monomer units derived from vinyl perfluoroalkyl or vinyl perfluoroalkylene oxide perfluorovinyl ether
WO2014204642A1 (en) 2013-06-18 2014-12-24 3M Innovative Properties Company Hydrophilic fluoroplastic substrates
US9126889B2 (en) 2013-09-04 2015-09-08 Honeywell International Inc. Fluorosurfactants having improved biodegradability
CN106414510B (en) 2013-11-26 2018-11-30 得凯莫斯公司弗罗里达有限公司 It is nucleated in the aqueous polymerization of fluorochemical monomer using polyalkylene oxide
JP5862751B2 (en) 2013-11-29 2016-02-16 ダイキン工業株式会社 Porous body, polymer electrolyte membrane, filter medium for filter and filter unit
EP3053937B1 (en) 2013-11-29 2019-02-27 Daikin Industries, Ltd. Modified polytetrafluoroethylene fine powder and uniaxially oriented porous body
EP3075768A4 (en) 2013-11-29 2017-06-21 Daikin Industries, Ltd. Biaxially-oriented porous film
EP3065209B1 (en) 2013-11-29 2019-04-10 Asahi Kasei Kabushiki Kaisha Polymer electrolyte film
EP3080174B1 (en) 2013-12-11 2019-09-18 3M Innovative Properties Company Highly fluorinated elastomers
EP2902424B1 (en) 2014-01-31 2020-04-08 3M Innovative Properties Company Tetrafluoroethene polymer dispersions stabilized with aliphatic non-ionic surfactants
WO2015134435A1 (en) 2014-03-06 2015-09-11 3M Innovative Properties Company Highly fluorinated elastomers
US10087322B2 (en) 2014-08-22 2018-10-02 3M Innovative Properties Company Fluorothermoplastic polymer
EP3183299B1 (en) 2014-08-22 2020-11-25 3M Innovative Properties Company Fluorothermoplastic polymer compositions
US10730980B2 (en) 2015-02-12 2020-08-04 3M Innovative Properties Company Tetrafluoroethylene/hexafluoropropylene copolymers including perfluoroalkoxyalkyl pendant groups
EP3256501B1 (en) 2015-02-12 2018-12-12 3M Innovative Properties Company Tetrafluoroethylene/hexafluoropropylene copolymers including perfluoroalkoxyalkyl pendant groups and methods of making and using the same
US10676555B2 (en) 2015-02-12 2020-06-09 3M Innovative Properties Company Tetrafluoroethylene copolymers having sulfonyl groups
EP3059265B1 (en) 2015-02-23 2020-10-07 3M Innovative Properties Company Peroxide curable fluoropolymers obtainable by polymerization with non-fluorinated emulsifiers
US10479067B2 (en) 2015-04-01 2019-11-19 3M Innovative Properties Company Multilayer articles comprising a release surface and methods thereof
EP3103836A1 (en) 2015-06-12 2016-12-14 3M Innovative Properties Company Fluoropolymer with improved transparency
US10590224B2 (en) 2015-07-13 2020-03-17 3M Innovative Properties Company Fluorinated block copolymers
US11155661B2 (en) 2015-09-23 2021-10-26 3M Innovative Properties Company Method of making a copolymer of tetrafluoroethylene having sulfonyl pendant groups
WO2017070172A1 (en) 2015-10-23 2017-04-27 3M Innovative Properties Company Composition including amorphous fluoropolymer and fluoroplastic particles and methods of making the same
WO2017083241A1 (en) 2015-11-10 2017-05-18 3M Innovative Properties Company Processing aid composition comprising a sulfonate-containing fluorinated polymer
EP3374422A1 (en) 2015-11-11 2018-09-19 3M Innovative Properties Company Conductive fluoropolymer compositions
WO2017094798A1 (en) * 2015-12-01 2017-06-08 旭硝子株式会社 Aqueous polytetrafluoroethylene dispersion
WO2017106119A1 (en) 2015-12-17 2017-06-22 3M Innovative Properties Company Amine-containing polymers, dispersions thereof and methods of making and using the same
CN105504133B (en) * 2015-12-31 2018-03-20 山东华夏神舟新材料有限公司 The preparation method of high speed extrusion level perfluoroethylene-propylene
JP6931652B2 (en) 2016-01-21 2021-09-08 スリーエム イノベイティブ プロパティズ カンパニー Fluoropolymer lamination process
EP3219771B1 (en) 2016-03-14 2019-02-06 3M Innovative Properties Company Fluoropolymer compositions with high content of inorganic material
CN109563206A (en) 2016-08-17 2019-04-02 3M创新有限公司 Tetrafluoroethene and perfluorinated allyl ethers copolymer
EP3284762A1 (en) 2016-08-17 2018-02-21 3M Innovative Properties Company Fluoropolymers comprising tetrafluoroethene and one or more perfluorinated alkyl allyl ether comonomers
US20210108063A1 (en) * 2016-12-01 2021-04-15 3M Innovative Properties Company Ethylene-tetrafluoroethylene copolymer dispersions and coated articles thereof
WO2018118956A1 (en) 2016-12-20 2018-06-28 3M Innovative Properties Company Composition including fluoropolymer and inorganic filler and method of making a three-dimensional article
JP2020504226A (en) 2017-01-18 2020-02-06 スリーエム イノベイティブ プロパティズ カンパニー Fluorinated block copolymer
WO2018136332A1 (en) 2017-01-18 2018-07-26 3M Innovative Properties Company Fluorinated block copolymers derived from cure-site monomers
JP2020504225A (en) 2017-01-18 2020-02-06 スリーエム イノベイティブ プロパティズ カンパニー Fluorinated block copolymers derived from nitrile cure site monomers
US20180287081A1 (en) * 2017-03-28 2018-10-04 Wuhan China Star Optoelectronics Technology Co., Ltd. Vertical channel organic thin-film transistor and manufacturing method thereof
JP6859455B2 (en) 2017-05-19 2021-04-14 スリーエム イノベイティブ プロパティズ カンパニー A method for producing a polyfluoroylated allyl ether and a compound related to the method.
DE202017003084U1 (en) 2017-06-13 2017-09-19 3M Innovative Properties Company Fluoropolymer dispersion
TW201908107A (en) 2017-07-19 2019-03-01 美商3M新設資產公司 Additive processing of fluoropolymer
WO2019055793A1 (en) 2017-09-14 2019-03-21 3M Innovative Properties Company Fluoropolymer dispersion, method for making the fluoropolymer dispersion, catalyst ink and polymer electrolyte membrane
JP7014976B2 (en) 2017-12-25 2022-02-15 ダイキン工業株式会社 Method for manufacturing polytetrafluoroethylene powder
US10953386B2 (en) 2017-12-29 2021-03-23 Mannon Water (Singapore) PTE. LTD. Filtration media for removing chloramine, chlorine, and ammonia, and method of making the same
EP3527634A1 (en) * 2018-02-15 2019-08-21 3M Innovative Properties Company Fluoropolymers and fluoropolymer dispersions
GB201807544D0 (en) 2018-05-09 2018-06-20 3M Innovative Properties Co Fluoropolymers with very low amounts of a fluorinated alkanoic acid or its salts
EP3824000A1 (en) 2018-07-20 2021-05-26 3M Innovative Properties Company Vinylidene fluoride fluoropolymers containing perfluorinated allyl ethers
JPWO2020022355A1 (en) 2018-07-23 2021-08-02 ダイキン工業株式会社 Polytetrafluoroethylene and stretched product
CN112703178B (en) 2018-08-30 2022-02-22 3M创新有限公司 Branched perfluorovinyl ether compound, process for producing the same, and fluoropolymer derived from branched perfluorovinyl ether compound
US20210355254A1 (en) 2018-10-03 2021-11-18 Daikin Industries, Ltd. Polytetrafluoroethylene production method
CN116041605A (en) 2018-10-03 2023-05-02 大金工业株式会社 Method for producing polytetrafluoroethylene
EP3640281A1 (en) 2018-10-19 2020-04-22 3M Innovative Properties Company Sprayable powder of fluoropolymer particles
US20220033673A1 (en) 2018-11-14 2022-02-03 3M Innovative Properties Company Copolymers of perfluorocycloaliphatic methyl vinyl ether
CN116836340A (en) 2018-11-19 2023-10-03 大金工业株式会社 Process for producing modified polytetrafluoroethylene and composition
EP3885406A4 (en) 2018-11-19 2022-08-10 Daikin Industries, Ltd. Composition and stretched body
CN113166305A (en) 2018-12-10 2021-07-23 大金工业株式会社 Tetrafluoroethylene polymer, air filter medium, filter element, and air filter unit
TW202033573A (en) 2018-12-17 2020-09-16 美商3M新設資產公司 Composition including curable fluoropolymer and curative and methods of making and using them
EP3919527A4 (en) 2019-02-01 2022-10-19 Daikin Industries, Ltd. Method for producing polytetrafluoroethylene
US20220119556A1 (en) 2019-02-07 2022-04-21 Daikin Industries, Ltd. Composition, stretched body and method of manufacturing thereof
WO2020183306A1 (en) 2019-03-12 2020-09-17 3M Innovative Properties Company Dispersible perfluorosulfonic acid ionomer compositions
US11548800B2 (en) 2019-04-26 2023-01-10 Geyser Remediation LLC Water purification apparatus and method
WO2020218620A1 (en) 2019-04-26 2020-10-29 ダイキン工業株式会社 Method for producing aqueous fluoropolymer dispersion, drainage treatment method, and aqueous fluoropolymer dispersion
JP7417129B2 (en) 2019-04-26 2024-01-18 ダイキン工業株式会社 Water treatment methods and compositions
CN113728015A (en) 2019-04-26 2021-11-30 大金工业株式会社 Method for producing aqueous fluoropolymer dispersion and aqueous fluoropolymer dispersion
JP7352804B2 (en) 2019-05-09 2023-09-29 ダイキン工業株式会社 Method for producing hollow fine particles and hollow fine particles
CN113906038A (en) 2019-06-04 2022-01-07 3M创新有限公司 Multifunctional fluorinated compounds, fluorinated polymers made therefrom, and related methods
US11452987B2 (en) 2019-06-19 2022-09-27 The Johns Hopkins University Contaminate sequestering coatings and methods of using the same
US20220235016A1 (en) 2019-06-28 2022-07-28 3M Innovative Properties Company Functionalized Triazine Compounds, Compositions Comprising Such Compounds and Cured Fluoropolymer Articles
US20220267483A1 (en) 2019-07-16 2022-08-25 Daikin Industries, Ltd. Method for producing fluorine-containing elastomer, and composition
EP4026854A4 (en) 2019-09-05 2024-01-17 Daikin Ind Ltd Polytetrafluoroethylene aqueous dispersion
EP4026855A4 (en) 2019-09-05 2023-09-20 Daikin Industries, Ltd. Composition and method for producing same
JP7265205B2 (en) 2019-10-03 2023-04-26 ダイキン工業株式会社 Polytetrafluoroethylene and method for producing the same
CN114729071A (en) 2019-11-19 2022-07-08 大金工业株式会社 Process for producing polytetrafluoroethylene
JP7352110B2 (en) 2019-11-19 2023-09-28 ダイキン工業株式会社 Method for producing fluoropolymer, method for producing polytetrafluoroethylene, method for producing perfluoroelastomer, and composition
EP4069755A1 (en) 2019-12-02 2022-10-12 3M Innovative Properties Company Dispersible particles of perfluorosulfonic acid ionomer
KR20220119048A (en) 2019-12-20 2022-08-26 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Fluorinated copolymers and compositions and articles comprising same
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EP4083085A4 (en) 2019-12-27 2024-01-24 Daikin Ind Ltd Method for producing fluorine-containing polymer, fluorine-containing elastomer and aqueous dispersion liquid
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CN116406351A (en) 2020-11-19 2023-07-07 大金工业株式会社 Fluorine-containing polymer and method for producing same
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Citations (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2516127A (en) * 1948-04-20 1950-07-25 Kellogg M W Co Separation of organic compounds
US2559752A (en) * 1951-03-06 1951-07-10 Du Pont Aqueous colloidal dispersions of polymers
US3271341A (en) * 1961-08-07 1966-09-06 Du Pont Aqueous colloidal dispersions of polymer
US3451908A (en) * 1966-07-19 1969-06-24 Montedison Spa Method for preparing polyoxyperfluoromethylenic compounds
US3555100A (en) * 1968-11-19 1971-01-12 Du Pont Decarbonylation of fluorinated acyl fluorides
US3635926A (en) * 1969-10-27 1972-01-18 Du Pont Aqueous process for making improved tetrafluoroethylene / fluoroalkyl perfluorovinyl ether copolymers
US3642742A (en) * 1969-04-22 1972-02-15 Du Pont Tough stable tetrafluoroethylene-fluoroalkyl perfluorovinyl ether copolymers
US3721696A (en) * 1970-11-27 1973-03-20 Montedison Spa Polyoxyperfluoromethylene compounds and process of their preparation
US3816524A (en) * 1972-08-31 1974-06-11 Dow Chemical Co Extraction of carboxylic acids from dilute aqueous solutions
US3882153A (en) * 1969-09-12 1975-05-06 Kureha Chemical Ind Co Ltd Method for recovering fluorinated carboxylic acid
US4005137A (en) * 1974-02-19 1977-01-25 Kali-Chemie Aktiengesellschaft Process for the purification and separation of perhaloalkanoic acids from mixtures thereof with perhaloalkanes
US4010156A (en) * 1973-04-19 1977-03-01 American Home Products Corporation Process for the rearrangement of penicillins to cephalosporins and intermediate compounds thereof
US4025709A (en) * 1974-09-24 1977-05-24 Produits Chimiques Ugine Kuhlmann Process for the polymerization of vinylidene fluoride
US4262101A (en) * 1976-08-31 1981-04-14 Hoechst Aktiengesellschaft Copolymers of tetrafluoroethylene and process for their manufacture
US4282162A (en) * 1979-02-02 1981-08-04 Hoechst Aktiengesellschaft Recovery of fluorinated emulsifying acids from basic anion exchangers
US4369266A (en) * 1979-03-01 1983-01-18 Hoechst Aktiengesellschaft Concentrated dispersions of fluorinated polymers and process for their preparation
US4380618A (en) * 1981-08-21 1983-04-19 E. I. Du Pont De Nemours And Company Batch polymerization process
US4381384A (en) * 1981-08-17 1983-04-26 E. I. Du Pont De Nemours And Company Continuous polymerization process
US4391940A (en) * 1979-12-12 1983-07-05 Hoechst Aktiengesellschaft Fluoropolymers with shell-modified particles, and processes for their preparation
US4439385A (en) * 1981-09-09 1984-03-27 Hoechst Aktiengesellschaft Continuous process for the agglomeration of PTFE powders in a liquid medium
US4446109A (en) * 1980-09-22 1984-05-01 Peabody Process Systems, Inc. System for dry scrubbing of flue gas
US4588796A (en) * 1984-04-23 1986-05-13 E. I. Du Pont De Nemours And Company Fluoroolefin polymerization process using fluoroxy compound solution as initiator
US4609497A (en) * 1985-03-14 1986-09-02 E. I. Du Pont De Nemours And Company Process for separating surfactants used in the manufacture of concentrated fluoropolymer dispersions
US4639337A (en) * 1985-03-14 1987-01-27 E. I. Du Pont De Nemours And Company Process for separating surfactants from liquid used in the manufacture of concentrated fluoropolymer dispersions
US4861845A (en) * 1988-03-10 1989-08-29 E. I. Du Pont De Nemours And Company Polymerization of fluoroolefins
US4864006A (en) * 1986-06-26 1989-09-05 Ausimont S.P.A. Process for the polymerization in aqueous dispersion of fluorinated monomers
US4987254A (en) * 1988-08-06 1991-01-22 Hoechst Aktiengesellschaft Fluorinated carboxylic acid fluorides
US5017480A (en) * 1987-08-10 1991-05-21 Ajimomoto Co., Inc. Process for recovering L-amino acid from fermentation liquors
US5090613A (en) * 1990-05-31 1992-02-25 Gold Star Co., Ltd. Method of manufacturing an anode assembly of a magnetron
US5285002A (en) * 1993-03-23 1994-02-08 Minnesota Mining And Manufacturing Company Fluorine-containing polymers and preparation and use thereof
US5312935A (en) * 1992-04-22 1994-05-17 Hoechst Aktiengesellschaft Purification of fluorinated carboxylic acids
US5442097A (en) * 1993-06-02 1995-08-15 Hoechst Aktiengesellschaft Process for the recovery of fluorinated carboxylic acids
US5498680A (en) * 1993-05-18 1996-03-12 Ausimont S.P.A. Polymerization process in aqueous emulsion of fuluorinated olefinic monomers
US5530078A (en) * 1993-10-20 1996-06-25 Hoechst Aktiengesellschaft Preparation of a modified polytetrafluoroethylene and use thereof
US5532310A (en) * 1995-04-28 1996-07-02 Minnesota Mining And Manufacturing Company Surfactants to create fluoropolymer dispersions in fluorinated liquids
US5656201A (en) * 1987-10-28 1997-08-12 Ausimont S.R.L. Aqueous microemulsions comprising functional perfluoropolyethers
US5763552A (en) * 1996-07-26 1998-06-09 E. I. Du Pont De Nemours And Company Hydrogen-containing flourosurfacant and its use in polymerization
US5789508A (en) * 1995-08-31 1998-08-04 E. I. Du Pont De Nemours And Company Polymerization process
US6013795A (en) * 1996-11-04 2000-01-11 3M Innovative Properties Company Alpha-branched fluoroalkylcarbonyl fluorides and their derivatives
US6025441A (en) * 1996-07-31 2000-02-15 Mitsubishi Rayon Company Ltd. Polytetrafluoroethylene-containing powder mixture, thermoplastic resin compositions including same and molded articles made therefrom
US6103844A (en) * 1998-06-08 2000-08-15 E. I. Du Pont De Nemours And Company Polymerization of fluoromonomers in carbon dioxide
US6245923B1 (en) * 1996-08-05 2001-06-12 Dyneon Gmbh Recovery of highly fluorinated carboxylic acids from the gaseous phase
US6255536B1 (en) * 1999-12-22 2001-07-03 Dyneon Llc Fluorine containing vinyl ethers
US6255384B1 (en) * 1995-11-06 2001-07-03 Alliedsignal, Inc. Method of manufacturing fluoropolymers
US20020040119A1 (en) * 2000-10-04 2002-04-04 Tang Phan L. Process for producing fluoroelastomers
US6395848B1 (en) * 1999-05-20 2002-05-28 E. I. Du Pont De Nemours And Company Polymerization of fluoromonomers
US6429258B1 (en) * 1999-05-20 2002-08-06 E. I. Du Pont De Nemours & Company Polymerization of fluoromonomers
US6436244B1 (en) * 1999-07-14 2002-08-20 Dyneon Gmbh Process for the elution of fluorinated emulsifiers
US20020114421A1 (en) * 2001-01-31 2002-08-22 Erbes John G. Jet pump beam lock
US6503988B1 (en) * 1995-11-09 2003-01-07 Daikin Industries, Ltd. Polytetrafluoroethylene fine powders and their use
US20030018148A1 (en) * 2001-05-02 2003-01-23 3M Innovative Properties Company Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers
US6512089B1 (en) * 2000-02-01 2003-01-28 3M Innovative Properties Company Process for working up aqueous dispersions of fluoropolymers
US6518442B1 (en) * 1998-06-02 2003-02-11 Dyneon Gmbh & Co., Kg Process for the recovery of fluorinated alkandic acids from wastewater
US6576703B2 (en) * 2000-02-22 2003-06-10 Ausimont S.P.A. Process for the preparation of aqueous dispersions of fluoropolymers
US6593416B2 (en) * 2000-02-01 2003-07-15 3M Innovative Properties Company Fluoropolymers
US20030153674A1 (en) * 2002-02-12 2003-08-14 Solvay Solexis S.P.A Fluoropolymer aqueous dispersions
US20040010156A1 (en) * 2000-08-11 2004-01-15 Masahiro Kondo Method of separating anionic fluorochemical surfactant
US6693152B2 (en) * 2001-05-02 2004-02-17 3M Innovative Properties Company Emulsifier free aqueous emulsion polymerization process for making fluoropolymers
US6703520B2 (en) * 2001-04-24 2004-03-09 3M Innovative Properties Company Process of preparing halogenated esters
US6706193B1 (en) * 1999-07-17 2004-03-16 3M Innovative Properties Company Method for recovering fluorinated emulsifiers from aqueous phases
US6715877B2 (en) * 2001-03-10 2004-04-06 Vasyl Molebny Method of measurement of wave aberrations of an eye and device for performing the same
US6720437B2 (en) * 2001-02-07 2004-04-13 E. I. Du Pont De Nemours And Company Fluorinated carboxylic acid recovery and reuse
US20040072977A1 (en) * 2001-03-26 2004-04-15 Ralph Kaulbach Aqueous emulsion polymerization process for producing fluoropolymers
US20040087703A1 (en) * 2002-10-31 2004-05-06 3M Innovative Properties Company Emulsifier free aqueous emulsion polymerization to produce copolymers of a fluorinated olefin and hydrocarbon olefin
US20040116742A1 (en) * 2002-12-17 2004-06-17 3M Innovative Properties Company Selective reaction of hexafluoropropylene oxide with perfluoroacyl fluorides
US20040143052A1 (en) * 2003-01-22 2004-07-22 3M Innovative Properties Company Aqueous fluoropolymer dispersion comprising a melt processible fluoropolymer and having a reduced amount of fluorinated surfactant
US6774164B2 (en) * 2000-09-22 2004-08-10 Dupont Dow Elastomers L.L.C. Process for producing fluoroelastomers with fluorinated anionic surfactants
US20050000904A1 (en) * 2003-07-02 2005-01-06 Remi Le Bec Process for the recovery of fluorosurfactants by active charcoal
US20050038177A1 (en) * 2002-03-20 2005-02-17 Asahi Glass Company Limited Aqueous polytetrafluoroethylene dispersion composition and process for its production
US6861466B2 (en) * 2003-02-28 2005-03-01 3M Innovative Properties Company Fluoropolymer dispersion containing no or little low molecular weight fluorinated surfactant
US20050070633A1 (en) * 2002-05-22 2005-03-31 3M Innovative Properties Company Process for reducing the amount of fluorinated surfactant in aqueous fluoropolymer dispersions
US20050090601A1 (en) * 2003-10-24 2005-04-28 3M Innovative Properties Company Aqueous dispersions of polytetrafluoroethylene particles
US20050090613A1 (en) * 2003-10-22 2005-04-28 Daikin Industries, Ltd. Process for preparing fluorine-containing polymer latex
US20050113507A1 (en) * 1998-12-11 2005-05-26 3M Innovative Properties Company Aqueous dispersions of fluoropolymers
US20050150833A1 (en) * 2002-06-19 2005-07-14 Asahi Glass Company Limited Method for recovering fluorine-containing emulsifier
US20050154104A1 (en) * 2003-12-04 2005-07-14 Solvay Solexis S.P.A. TFE copolymers
US20050171381A1 (en) * 2002-09-30 2005-08-04 Daikin Industries, Ltd. Process for preparing fluorocarboxylic acids
US20050173347A1 (en) * 2004-02-05 2005-08-11 3M Innovative Properties Company Removal of fluorinated surfactants from waste water
US20050177000A1 (en) * 2004-02-05 2005-08-11 3M Innovative Properties Company Method of recovering fluorinated acid surfactants from adsorbent particles loaded therewith
US20060041051A1 (en) * 2002-11-29 2006-02-23 Yasukazu Nakatani Method for purification of aqueous fluoropolymer emulsions, purified emulsions, and fluorine-containing finished articles
US7045571B2 (en) * 2001-05-21 2006-05-16 3M Innovative Properties Company Emulsion polymerization of fluorinated monomers
US7045591B2 (en) * 2000-08-30 2006-05-16 Hoffmann-La Roche Inc. Selective cyclic peptides with melanocortin-4 receptor (MC4-R) agonist activity
US20070015937A1 (en) * 2005-07-15 2007-01-18 3M Innovative Properties Company Process for recovery of fluorinated carboxylic acid surfactants from exhaust gas
US20070117915A1 (en) * 2004-07-28 2007-05-24 Asahi Glass Company, Limited Fluoropolymer latex, process for its production, and fluoropolymer
US20070135558A1 (en) * 2003-10-31 2007-06-14 Nobuhiko Tsuda Process for producing aqueous fluoropolymer dispersion and aqueous fluoropolymer dispersion
US20070149733A1 (en) * 2003-12-25 2007-06-28 Masao Otsuka Process for preparing fluoropolymer
US20070155891A1 (en) * 2003-12-09 2007-07-05 Daikin Industries, Ltd. Water base dispersion of fluorinated polymer and process for producing the same

Family Cites Families (157)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US625536A (en) * 1899-05-23 Johann jakob brack
FR814839A (en) 1935-12-13 1937-06-30 Du Pont Process for the separation of constituents from complexes containing halides
GB642025A (en) 1947-10-31 1950-08-23 Du Pont Electrodecantation of dilute suspensions
US2713593A (en) * 1953-12-21 1955-07-19 Minnesota Mining & Mfg Fluorocarbon acids and derivatives
NL102460C (en) 1957-01-11
US3179614A (en) * 1961-03-13 1965-04-20 Du Pont Polyamide-acids, compositions thereof, and process for their preparation
US3142665A (en) * 1960-07-26 1964-07-28 Du Pont Novel tetrafluoroethylene resins and their preparation
US3037953A (en) * 1961-04-26 1962-06-05 Du Pont Concentration of aqueous colloidal dispersions of polytetrafluoroethylene
BE621663A (en) 1961-08-25
US3345317A (en) 1963-04-04 1967-10-03 Thiokol Chemical Corp Emulsion polymerization of tetrafluoroethylene using trifluorotrichloroethane as emulsion stabilizer
US3260691A (en) * 1963-05-20 1966-07-12 Monsanto Co Coating compositions prepared from condensation products of aromatic primary diamines and aromatic tricarboxylic compounds
US3654353A (en) 1964-10-23 1972-04-04 Weyerhaeuser Co Method of treating spent pulp liquors
US3315201A (en) * 1965-03-31 1967-04-18 Bailey Meter Co Strain transducer
US3391099A (en) * 1966-04-25 1968-07-02 Du Pont Polymerization process
US3489595A (en) * 1966-12-22 1970-01-13 Du Pont Coating compositions containing perfluorohalocarbon polymer,phosphoric acid and aluminum oxide,boron oxide or aluminum phosphate
US3790403A (en) * 1972-01-13 1974-02-05 Du Pont Glass fabric coated with crack-free fluorocarbon resin coating and process for preparing
US3997599A (en) 1972-08-31 1976-12-14 The Dow Chemical Company Extraction of carboxylic acids from dilute aqueous solutions
US4016345A (en) * 1972-12-22 1977-04-05 E. I. Du Pont De Nemours And Company Process for polymerizing tetrafluoroethylene in aqueous dispersion
US3855191A (en) 1973-04-04 1974-12-17 Du Pont Polytetrafluoroethylene molding powders of tetrafluoroethylene and perfluoro (alkyl vinyl ether) copolymer
CA1031094A (en) 1973-11-19 1978-05-09 Imperial Chemical Industries Limited Polysulphone-fluorocarbon coating compositions
DE2432473A1 (en) 1974-07-06 1976-01-22 Hoechst Ag PROCESS FOR THE PRODUCTION OF LOW FATTY ACIDS AND HALOGEN FATTY ACIDS
US4123401A (en) 1975-07-21 1978-10-31 E. I. Du Pont De Nemours And Company Finishes having improved scratch resistance prepared from compositions of fluoropolymer, mica particles or metal flake, a polymer of monoethylenically unsaturated monomers and a liquid carrier
US4049863A (en) 1975-07-31 1977-09-20 E. I. Du Pont De Nemours And Company Fluoropolymer primer having improved scratch resistance
DE2546320A1 (en) 1975-10-16 1977-04-21 Akad Wissenschaften Ddr Perfluoro alkane carboxylic acid purifcn. - by extn. of potassium salt from aq. soln. using water miscible organic solvent
US4060535A (en) 1976-08-31 1977-11-29 Tenneco Chemicals, Inc. Process for the production of metal salts of organic acids
JPS5349090A (en) * 1976-10-15 1978-05-04 Asahi Glass Co Ltd Preparation of fluorinated plymer containing ion exchange group
AU507930B2 (en) 1977-01-25 1980-03-06 Ici Ltd. Coating with polytetrafluoroethylene-polyethersulphone composition
US4252859A (en) * 1978-10-31 1981-02-24 E. I. Du Pont De Nemours And Company Fluoropolymer blend coating compositions containing copolymers of perfluorinated polyvinyl ether
US4544458A (en) 1978-11-13 1985-10-01 E. I. Du Pont De Nemours And Company Fluorinated ion exchange polymer containing carboxylic groups, process for making same, and film and membrane thereof
CA1132397A (en) 1979-02-28 1982-09-28 Hendrik E. Kokelenberg Fluorine-containing surfactants and their use in hydrophilic colloid coating compositions and light-sensitive silver halide materials
US4353950A (en) 1979-07-06 1982-10-12 E. I. Du Pont De Nemours And Company Stain-resistant cookware multi-layer coating system comprising pigments and a transluscent outer layer
JPS5645911A (en) * 1979-09-25 1981-04-25 Asahi Glass Co Ltd Production of ion-exchangeable fluorinated polymer
US4287112A (en) 1979-11-16 1981-09-01 E. I. Du Pont De Nemours And Company Coating of poly(arylene sulfide), fluoropolymer and aluminum flake
US4832879A (en) * 1980-03-04 1989-05-23 Basf Aktiengesellchaft Substituted 3-fluoroalkoxybenzoyl halides and their preparation
EP0037602B1 (en) 1980-04-09 1984-06-13 Agfa-Gevaert N.V. Photographic elements containing novel cyan-forming colour couplers
JPS58174407A (en) 1982-03-08 1983-10-13 Daikin Ind Ltd Fluorine-containing copolymer having improved extrudability
US4425448A (en) * 1982-05-20 1984-01-10 E. I. Du Pont De Nemours & Co. Polytetrafluoroethylene resin with degradation retarder
US4605773A (en) * 1982-08-10 1986-08-12 Diamond Shamrock Chemicals Company Low-foaming, pH sensitive, alkylamine polyether surface active agents and methods for using
DE3303779A1 (en) * 1983-02-04 1984-08-16 Hoechst Ag, 6230 Frankfurt METHOD FOR PRODUCING A CATALYTICALLY EFFECTIVE ELECTRODE MATERIAL FOR OXYGEN CONSUMPTION ELECTRODES
JPS59199774A (en) 1983-04-27 1984-11-12 Daikin Ind Ltd Primer composition
DE3437278A1 (en) 1984-10-11 1986-04-17 Hoechst Ag, 6230 Frankfurt CONCENTRATED, AQUEOUS DISPERSIONS OF VINYLIDE FLUORIDE POLYMERS AND METHOD FOR THE PRODUCTION THEREOF
US4621116A (en) 1984-12-07 1986-11-04 E. I. Du Pont De Nemours And Company Process for copolymerization of tetrafluoroethylene in the presence of a dispersing agent comprising a perfluoroalkoxybenzene sulfonic acid or salt
US4623487A (en) 1985-03-14 1986-11-18 E. I. Du Pont De Nemours & Company Process for recovery of fluorosurfactants
JPS6289713A (en) 1985-10-12 1987-04-24 Daikin Ind Ltd Novel fluoroelastomer and production thereof
EP0222945B1 (en) 1985-11-08 1992-01-02 E.I. Du Pont De Nemours And Company Melt-processible tetrafluoroethylene/perfluoroolefin copolymers and processes for preparing them
US4847135A (en) * 1986-01-21 1989-07-11 Kolbenschmidt Aktiengesellschaft Composite material for sliding surface bearings
IT1189092B (en) 1986-04-29 1988-01-28 Ausimont Spa POLYMERIZATION PROCESS IN WATER DISPERSION OF FLUORINATED MONOMERS
US5198491A (en) * 1986-07-21 1993-03-30 Daikin Industries Ltd. Cooking utensils surface coated with tetrafluoroethlene base polymer
IT1215418B (en) 1987-04-10 1990-02-08 Ausimont Spa PERFLUOROALKANS OBTAINED BY PHOTOCHEMICAL FLUORURATION AND THEIR USE AS POLYMERIZATION INITIATORS.
US5153322A (en) 1987-10-30 1992-10-06 Minnesota Mining And Manufacturing Company Perfluoro (cycloaliphatic methyleneoxyalkylene) carbonyl fluorides and derivatives thereof
US4925709A (en) * 1988-03-18 1990-05-15 Itzhak Shmueli Net of plastic rings connected by connector means
KR960003930B1 (en) 1988-05-13 1996-03-23 아사히가라스 가부시끼가이샤 Process for preparing an aqueous dispersion, aqueous dispersion and aqueous coating composition
DE3828063A1 (en) 1988-08-18 1990-02-22 Hoechst Ag SUBSTITUTED (2-HALOALKOXY-1.1.2-TRIFLUORAETHOXY) STYROLE, PROCESS FOR THEIR PRODUCTION AND THEIR USE
US5160791A (en) 1990-12-12 1992-11-03 E. I. Du Pont De Nemours And Company Non-stick coating system with two perfluorocarbon resins in topcoat for concentration gradient
US5230961A (en) * 1990-12-12 1993-07-27 E. I. Du Pont De Nemours And Company Non-stick coating system with PTFE-FEP for concentration gradient
US5223343A (en) * 1990-12-12 1993-06-29 E. I. Du Pont De Nemours And Company Non-stick coating system with high and low melt viscosity PTFE for concentration gradient
US5168107A (en) 1990-12-12 1992-12-01 E. I. Du Pont De Nemours And Company Non-stick coating system with PTFE of two low melt viscosities for concentration gradient
DE4124134A1 (en) 1991-07-20 1993-01-21 Hoechst Ag CONCENTRATED, AQUEOUS DISPERSIONS OF TETRAFLUORETHYLENE POLYMERS, METHOD FOR THE PRODUCTION AND USE THEREOF
JP3198542B2 (en) 1991-07-24 2001-08-13 ダイキン工業株式会社 Composition for coating modified polytetrafluoroethylene
US5182342A (en) * 1992-02-28 1993-01-26 E. I. Du Pont De Nemours And Company Hydrofluorocarbon solvents for fluoromonomer polymerization
US5453477A (en) 1992-05-01 1995-09-26 Alliedsignal Inc. Process of polymerizing chloroetrifluoroethylene with alkyl hydroperoxide and metal metabisulfite
US5272186A (en) 1992-05-01 1993-12-21 E. I. Du Pont De Nemours And Company Concentration of fluoropolymer dispersions using acrylic polymers of high acid content
US5229480A (en) * 1992-09-03 1993-07-20 E. I. Du Pont De Nemours And Company Vinyl fluoride polymerization
DE4233824A1 (en) 1992-10-08 1994-04-14 Hoechst Ag Process for working up aqueous dispersions of fluorothermoplastics
US5789083A (en) 1992-12-23 1998-08-04 E. I. Du Pont De Nemours And Company Aqueous fluoropolymer primer for smooth substrates
US5721053A (en) * 1992-12-23 1998-02-24 E. I. Du Pont De Nemours And Company Post-formable non-stick roller coated smooth substrates
US5667846A (en) 1992-12-23 1997-09-16 E. I. Du Pont De Nemours And Company Roller coating to make post-formable non-stick smooth substrates
DE4305619A1 (en) 1993-02-24 1994-08-25 Hoechst Ag Fine-particle dispersions of thermoplastic fluoropolymers
JP3172983B2 (en) 1993-09-20 2001-06-04 ダイキン工業株式会社 Aqueous dispersion of vinylidene fluoride polymer and process for producing the same
US5488142A (en) * 1993-10-04 1996-01-30 Minnesota Mining And Manufacturing Company Fluorination in tubular reactor system
WO1995010541A1 (en) * 1993-10-12 1995-04-20 Asahi Kasei Kogyo Kabushiki Kaisha Perfluorocarbon copolymer having functional groups and process for producing the same
DE4340943A1 (en) 1993-12-01 1995-06-08 Hoechst Ag Aqueous dispersion of fluoropolymers, their production and use for coatings
DE69529389T2 (en) * 1994-04-18 2003-05-22 Yasuhiro Koike OPTICAL RESIN WITH BREAKING INDEX DISTRIBUTION AND THEIR PRODUCTION METHOD
IT1269517B (en) * 1994-05-19 1997-04-01 Ausimont Spa FLUORINATED POLYMERS AND COPOLYMERS CONTAINING CYCLIC STRUCTURES
JP2829706B2 (en) 1994-07-11 1998-12-02 三井・デュポンフロロケミカル株式会社 Aqueous fluoropolymer emulsion and method for producing the same
JP3298321B2 (en) 1994-08-31 2002-07-02 ダイキン工業株式会社 Aqueous dispersion of vinylidene fluoride-based copolymer, aqueous dispersion of vinylidene fluoride-based seed polymer and methods for producing them
US5478651A (en) 1994-10-31 1995-12-26 E. I. Du Pont De Nemours And Company Process for making fluoropolymer finish composition
US5562991A (en) 1994-10-31 1996-10-08 E. I. Du Pont De Nemours And Company Universal Primer for non-stick finish
TW363075B (en) 1994-11-01 1999-07-01 Daikin Ind Ltd Fluoride polymer compound painting and coating method thereof
IT1270703B (en) 1994-11-17 1997-05-07 Ausimont Spa MICROEMULSIONS OF FLUOROPOLYXIALKYLENES IN A MIXTURE WITH HYDROCARBONS, AND THEIR USE IN PROCESSES OF (CO) POLYMERIZATION OF FLUORINATED MONOMERS
US5895799A (en) * 1995-01-18 1999-04-20 W. L. Gore & Associates, Inc. Microemulsion polymerization process for the production of small polytetrafluoroethylene polymer particles
EP0804493B1 (en) * 1995-01-18 1999-08-18 W.L. Gore & Associates, Inc. Microemulsion polymerization systems for fluoromonomers
US5478905A (en) 1995-02-06 1995-12-26 E. I. Du Pont De Nemours And Company Amorphous tetrafluoroethylene/hexafluoropropylene copolymers
EP0731081B1 (en) 1995-03-09 1998-04-15 Dyneon GmbH Recovery of highly fluorinated carboxylic acids from gaseous phase
JP3346090B2 (en) 1995-03-31 2002-11-18 ダイキン工業株式会社 Polytetrafluoroethylene aqueous dispersion composition and use thereof
US5688884A (en) 1995-08-31 1997-11-18 E. I. Du Pont De Nemours And Company Polymerization process
IT1276072B1 (en) 1995-10-31 1997-10-24 Ausimont Spa PROCESS OF (CO) POLYMERIZATION OF FLUORINATED MONOMERS TO OBTAIN HYDROGEN CONTAINING POLYMERS
JPH108041A (en) 1996-06-21 1998-01-13 Daikin Ind Ltd Water dispersion type fluorine-based water and oil-repellent
IT1295535B1 (en) 1996-07-01 1999-05-12 Ausimont Spa VINYLIDENFLUORIDE (VDF) POLYMERIZATION PROCESS
EP0911357B1 (en) * 1997-02-13 2005-04-27 Daikin Industries, Ltd. Method for concentrating aqueous fluoropolymer dispersion
IT1290428B1 (en) * 1997-03-21 1998-12-03 Ausimont Spa FLUORINATED FATS
EP0978537B1 (en) * 1997-04-30 2004-09-15 Daikin Industries, Ltd. Aqueous dispersion composition and coated articles
US6267865B1 (en) * 1997-05-02 2001-07-31 3M Innovative Properties Company Electrochemical fluorination using interrupted current
TW494125B (en) 1997-07-11 2002-07-11 Rohm And Haas Compary Preparation of fluorinated polymers
DE19732945A1 (en) 1997-07-31 1999-02-04 Weilburger Lackfabrik Jakob Gr Item with a non-stick coating
DE69933545T2 (en) 1998-02-24 2007-06-21 Asahi Glass Co., Ltd. Aqueous polytetrafluoroethylene dispersion composition
DE19824614A1 (en) 1998-06-02 1999-12-09 Dyneon Gmbh Process for the recovery of fluorinated alkanoic acids from waste water
ITMI981519A1 (en) 1998-07-02 2000-01-02 Ausimont Spa POLYMERIZATION PROCESS OF TFE
KR100616797B1 (en) 1998-08-20 2006-08-28 아사히 가라스 가부시키가이샤 Aqueous dispersion of fluorocopolymer and composition for water-based coating material
JP2000128934A (en) 1998-08-20 2000-05-09 Asahi Glass Co Ltd Aqueous dispersion of fluorine-based copolymer
CN1215085C (en) 1998-10-13 2005-08-17 大金工业株式会社 Process for producing fluoropolymer
MXPA01008840A (en) 1999-03-02 2002-05-14 Du Pont Free radical polymerization method for fluorinated copolymers.
AU4297000A (en) * 1999-04-23 2000-11-10 Carsten Dusterhoft Automated method and device for the non-cutting shaping of body
ITMI991269A1 (en) 1999-06-08 2000-12-08 Ausimont Spa MIXTURES OF FLUOROPOLYMER DISPERSIONS
DE19926622A1 (en) 1999-06-11 2000-12-14 Bayer Ag Thermoplastic molding compounds
RU2158274C1 (en) 1999-08-24 2000-10-27 ОАО "Кирово-Чепецкий химический комбинат имени Б.П.Константинова" Method of preparing elastic copolymer of vinylidene fluoride with 25-30 mole % of hexafluoropropylene
US6459405B1 (en) 1999-09-07 2002-10-01 Lucent Technologies Inc. Satellite-based location system employing knowledge-based sequential signal search strategy
ATE417909T1 (en) 1999-10-29 2009-01-15 Asahi Glass Co Ltd WATER AND OIL REPELLENT COMPOSITION DISPERSED IN WATER AND METHOD FOR THE PRODUCTION THEREOF
DE19953285A1 (en) 1999-11-05 2001-05-10 Dyneon Gmbh Process for the recovery of fluorinated emulsifiers
US6710123B1 (en) * 1999-11-12 2004-03-23 Atofina Chemicals, Inc. Fluoropolymers containing organo-silanes and methods of making the same
US6482979B1 (en) 1999-12-22 2002-11-19 Dyneon Llc Perfluorinated acid fluorides and preparation thereof
US6677414B2 (en) * 1999-12-30 2004-01-13 3M Innovative Properties Company Aqueous emulsion polymerization process for the manufacturing of fluoropolymers
AU2811501A (en) * 2000-03-28 2001-10-04 Sumitomo Chemical Company, Limited Amidine compounds and their use as pesticides
US6794550B2 (en) * 2000-04-14 2004-09-21 3M Innovative Properties Company Method of making an aqueous dispersion of fluoropolymers
DE10018853C2 (en) 2000-04-14 2002-07-18 Dyneon Gmbh Production of aqueous dispersions of fluoropolymers
JP5055652B2 (en) 2000-08-11 2012-10-24 ダイキン工業株式会社 Method for recovering fluorine-containing surfactant
US6846570B2 (en) * 2000-08-17 2005-01-25 Whitford Corporation Multiple coat non-stick coating system and articles coated with same
AU2001285453A1 (en) * 2000-08-17 2002-02-25 Whitford Corporation Single coat non-stick coating system and articles coated with same
US6632508B1 (en) 2000-10-27 2003-10-14 3M Innovative Properties Company Optical elements comprising a polyfluoropolyether surface treatment
JP2002179870A (en) 2000-12-11 2002-06-26 Daikin Ind Ltd Eco-friendly aqueous dispersion of fluorine-containing polymer having excellent dispersion stability
US6730760B2 (en) 2001-01-31 2004-05-04 3M Innovative Properties Company Perfluoroelastomers having a low glass transition temperature and method of making them
EP1241041B1 (en) 2001-03-14 2004-10-20 Conception et Développement Michelin S.A. Vehicle with super-capacitor for regenerative braking
US6761964B2 (en) * 2001-04-02 2004-07-13 E. I. Du Pont De Nemours And Company Fluoropolymer non-stick coatings
JP2002308914A (en) 2001-04-17 2002-10-23 Daikin Ind Ltd Method for producing fluorine-containing polymer latex
JP2002317003A (en) 2001-04-19 2002-10-31 Daikin Ind Ltd Method for producing florine-containing polymer latex
US6737489B2 (en) * 2001-05-21 2004-05-18 3M Innovative Properties Company Polymers containing perfluorovinyl ethers and applications for such polymers
US20030125421A1 (en) * 2001-08-03 2003-07-03 Hermann Bladel Aqueous dispersions of fluoropolymers
JP2003043625A (en) 2001-08-03 2003-02-13 Konica Corp Photothermographic image forming material having improved scratch resistance
US6689854B2 (en) * 2001-08-23 2004-02-10 3M Innovative Properties Company Water and oil repellent masonry treatments
US7279522B2 (en) 2001-09-05 2007-10-09 3M Innovative Properties Company Fluoropolymer dispersions containing no or little low molecular weight fluorinated surfactant
JP3900883B2 (en) 2001-10-05 2007-04-04 ダイキン工業株式会社 Method for producing fluoropolymer latex
US20040101561A1 (en) 2002-11-13 2004-05-27 Jafari Masoud R. Combinations of viscoelastics for use during surgery
BRPI0215428A8 (en) 2002-01-04 2018-08-14 Du Pont aqueous dispersion, aqueous dispersion coating composition, coated substrates and self-supporting film
JP4191929B2 (en) 2002-01-25 2008-12-03 株式会社ジェムコ Method for recovering fluorine-containing emulsifier
JP2003284921A (en) 2002-03-28 2003-10-07 Asahi Glass Co Ltd Recovery method for fluorine-containing emulsifier
US6822059B2 (en) 2002-04-05 2004-11-23 3M Innovative Properties Company Dispersions containing bicomponent fluoropolymer particles and use thereof
EP2365008B1 (en) 2002-06-17 2016-10-19 Daikin Industries, Ltd. Fluoropolymer dispersion and process for producing fluoropolymer dispersion
AU2003204534A1 (en) * 2002-06-28 2004-01-22 James E Cotter Apparatus for detecting metal objects being put into a trash can
JP4030377B2 (en) * 2002-07-24 2008-01-09 白光株式会社 Electrical component removal device
JP2004146796A (en) * 2002-09-30 2004-05-20 Seiko Epson Corp Method of forming film pattern, thin-film forming apparatus, electrically conductive film wiring, electrooptic device, electronic apparatus, and non-contact card medium
US6729437B1 (en) * 2002-10-30 2004-05-04 Gregory L. Apple Tree step tool and method
US6841616B2 (en) 2003-03-28 2005-01-11 Arkema Inc. Polymerization of halogen-containing monomers using siloxane surfactant
US6869997B2 (en) * 2003-05-06 2005-03-22 Arkema, Inc. Polymerization of fluoromonomers using a 3-allyloxy-2-hydroxy-1-propanesulfonic acid salt as surfactant
JP2004359870A (en) 2003-06-05 2004-12-24 Daikin Ind Ltd Surfactant and fluorine-containing polymer manufacturing method, and fluorine-containing polymer aqueous dispersion
JP2004358397A (en) 2003-06-05 2004-12-24 Daikin Ind Ltd Surfactant, production method of fluorine-containing polymer, and fluorine-containing polymer aqueous dispersion
JP4289034B2 (en) 2003-06-19 2009-07-01 旭硝子株式会社 Polytetrafluoroethylene aqueous dispersion composition and process for producing the same
US7589234B2 (en) 2003-07-02 2009-09-15 Daikin Industries, Ltd. Fluoroalkyl carboxylic acid derivative, method for producing fluorine-containing polymer, and aqueous dispersion of fluorine-containing polymer
JP2005105045A (en) 2003-09-29 2005-04-21 Dainippon Ink & Chem Inc Surfactant composition
ITMI20032050A1 (en) * 2003-10-21 2005-04-22 Solvay Solexis Spa PROCESS FOR THE PREPARATION OF FLUOROPOLYMER DISPERSERS.
ATE529451T1 (en) * 2003-11-17 2011-11-15 3M Innovative Properties Co AQUEOUS PTFE DISPERSIONS WITH A LOW CONTENT OF FLUORINATED EMULSIFIERS
WO2005065800A1 (en) 2003-12-30 2005-07-21 Daikin Industries, Ltd. Process for separating fluorine-containing surfactant
EP1570917B1 (en) 2004-03-01 2009-06-10 3M Innovative Properties Company Method of coating a substrate with a fluoropolymer dispersion
FR2871469A1 (en) 2004-06-10 2005-12-16 Arkema Sa PROCESS FOR PRODUCING FLUORINE POLYMER
PL1614731T3 (en) * 2004-07-05 2009-02-27 3M Innovative Properties Co Primer coating of PTFE for metal substrates
US7304101B2 (en) * 2004-07-19 2007-12-04 3M Innovative Properties Company Method of purifying a dispersion of ionic fluoropolymer
JP4838799B2 (en) 2004-08-11 2011-12-14 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Removal of fluorosurfactants from aqueous fluoropolymer dispersions using sorbent pouches
US8338518B2 (en) * 2005-06-10 2012-12-25 Arkema Inc. Aqueous process for making a stable fluoropolymer dispersion

Patent Citations (99)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2516127A (en) * 1948-04-20 1950-07-25 Kellogg M W Co Separation of organic compounds
US2559752A (en) * 1951-03-06 1951-07-10 Du Pont Aqueous colloidal dispersions of polymers
US3271341A (en) * 1961-08-07 1966-09-06 Du Pont Aqueous colloidal dispersions of polymer
US3451908A (en) * 1966-07-19 1969-06-24 Montedison Spa Method for preparing polyoxyperfluoromethylenic compounds
US3555100A (en) * 1968-11-19 1971-01-12 Du Pont Decarbonylation of fluorinated acyl fluorides
US3642742A (en) * 1969-04-22 1972-02-15 Du Pont Tough stable tetrafluoroethylene-fluoroalkyl perfluorovinyl ether copolymers
US3882153A (en) * 1969-09-12 1975-05-06 Kureha Chemical Ind Co Ltd Method for recovering fluorinated carboxylic acid
US3635926A (en) * 1969-10-27 1972-01-18 Du Pont Aqueous process for making improved tetrafluoroethylene / fluoroalkyl perfluorovinyl ether copolymers
US3721696A (en) * 1970-11-27 1973-03-20 Montedison Spa Polyoxyperfluoromethylene compounds and process of their preparation
US3816524A (en) * 1972-08-31 1974-06-11 Dow Chemical Co Extraction of carboxylic acids from dilute aqueous solutions
US4010156A (en) * 1973-04-19 1977-03-01 American Home Products Corporation Process for the rearrangement of penicillins to cephalosporins and intermediate compounds thereof
US4005137A (en) * 1974-02-19 1977-01-25 Kali-Chemie Aktiengesellschaft Process for the purification and separation of perhaloalkanoic acids from mixtures thereof with perhaloalkanes
US4025709A (en) * 1974-09-24 1977-05-24 Produits Chimiques Ugine Kuhlmann Process for the polymerization of vinylidene fluoride
US4262101A (en) * 1976-08-31 1981-04-14 Hoechst Aktiengesellschaft Copolymers of tetrafluoroethylene and process for their manufacture
US4282162A (en) * 1979-02-02 1981-08-04 Hoechst Aktiengesellschaft Recovery of fluorinated emulsifying acids from basic anion exchangers
US4369266A (en) * 1979-03-01 1983-01-18 Hoechst Aktiengesellschaft Concentrated dispersions of fluorinated polymers and process for their preparation
US4391940A (en) * 1979-12-12 1983-07-05 Hoechst Aktiengesellschaft Fluoropolymers with shell-modified particles, and processes for their preparation
US4446109A (en) * 1980-09-22 1984-05-01 Peabody Process Systems, Inc. System for dry scrubbing of flue gas
US4381384A (en) * 1981-08-17 1983-04-26 E. I. Du Pont De Nemours And Company Continuous polymerization process
US4380618A (en) * 1981-08-21 1983-04-19 E. I. Du Pont De Nemours And Company Batch polymerization process
US4439385A (en) * 1981-09-09 1984-03-27 Hoechst Aktiengesellschaft Continuous process for the agglomeration of PTFE powders in a liquid medium
US4588796A (en) * 1984-04-23 1986-05-13 E. I. Du Pont De Nemours And Company Fluoroolefin polymerization process using fluoroxy compound solution as initiator
US4609497A (en) * 1985-03-14 1986-09-02 E. I. Du Pont De Nemours And Company Process for separating surfactants used in the manufacture of concentrated fluoropolymer dispersions
US4639337A (en) * 1985-03-14 1987-01-27 E. I. Du Pont De Nemours And Company Process for separating surfactants from liquid used in the manufacture of concentrated fluoropolymer dispersions
US4864006A (en) * 1986-06-26 1989-09-05 Ausimont S.P.A. Process for the polymerization in aqueous dispersion of fluorinated monomers
US5017480A (en) * 1987-08-10 1991-05-21 Ajimomoto Co., Inc. Process for recovering L-amino acid from fermentation liquors
US5656201A (en) * 1987-10-28 1997-08-12 Ausimont S.R.L. Aqueous microemulsions comprising functional perfluoropolyethers
US4861845A (en) * 1988-03-10 1989-08-29 E. I. Du Pont De Nemours And Company Polymerization of fluoroolefins
US4987254A (en) * 1988-08-06 1991-01-22 Hoechst Aktiengesellschaft Fluorinated carboxylic acid fluorides
US5090613A (en) * 1990-05-31 1992-02-25 Gold Star Co., Ltd. Method of manufacturing an anode assembly of a magnetron
US5312935A (en) * 1992-04-22 1994-05-17 Hoechst Aktiengesellschaft Purification of fluorinated carboxylic acids
US5285002A (en) * 1993-03-23 1994-02-08 Minnesota Mining And Manufacturing Company Fluorine-containing polymers and preparation and use thereof
US5498680A (en) * 1993-05-18 1996-03-12 Ausimont S.P.A. Polymerization process in aqueous emulsion of fuluorinated olefinic monomers
US5442097A (en) * 1993-06-02 1995-08-15 Hoechst Aktiengesellschaft Process for the recovery of fluorinated carboxylic acids
US5591877A (en) * 1993-06-02 1997-01-07 Hoechst Ag Process for the recovery of fluorinated carboxylic acids
US5530078A (en) * 1993-10-20 1996-06-25 Hoechst Aktiengesellschaft Preparation of a modified polytetrafluoroethylene and use thereof
US5532310A (en) * 1995-04-28 1996-07-02 Minnesota Mining And Manufacturing Company Surfactants to create fluoropolymer dispersions in fluorinated liquids
US5789508A (en) * 1995-08-31 1998-08-04 E. I. Du Pont De Nemours And Company Polymerization process
US6255384B1 (en) * 1995-11-06 2001-07-03 Alliedsignal, Inc. Method of manufacturing fluoropolymers
US6365684B1 (en) * 1995-11-06 2002-04-02 Alliedsignal Inc. Method of manufacturing fluoropolymers
US6503988B1 (en) * 1995-11-09 2003-01-07 Daikin Industries, Ltd. Polytetrafluoroethylene fine powders and their use
US5763552A (en) * 1996-07-26 1998-06-09 E. I. Du Pont De Nemours And Company Hydrogen-containing flourosurfacant and its use in polymerization
US6025441A (en) * 1996-07-31 2000-02-15 Mitsubishi Rayon Company Ltd. Polytetrafluoroethylene-containing powder mixture, thermoplastic resin compositions including same and molded articles made therefrom
US6245923B1 (en) * 1996-08-05 2001-06-12 Dyneon Gmbh Recovery of highly fluorinated carboxylic acids from the gaseous phase
US6013795A (en) * 1996-11-04 2000-01-11 3M Innovative Properties Company Alpha-branched fluoroalkylcarbonyl fluorides and their derivatives
US6518442B1 (en) * 1998-06-02 2003-02-11 Dyneon Gmbh & Co., Kg Process for the recovery of fluorinated alkandic acids from wastewater
US6103844A (en) * 1998-06-08 2000-08-15 E. I. Du Pont De Nemours And Company Polymerization of fluoromonomers in carbon dioxide
US20050113507A1 (en) * 1998-12-11 2005-05-26 3M Innovative Properties Company Aqueous dispersions of fluoropolymers
US6429258B1 (en) * 1999-05-20 2002-08-06 E. I. Du Pont De Nemours & Company Polymerization of fluoromonomers
US6395848B1 (en) * 1999-05-20 2002-05-28 E. I. Du Pont De Nemours And Company Polymerization of fluoromonomers
US6436244B1 (en) * 1999-07-14 2002-08-20 Dyneon Gmbh Process for the elution of fluorinated emulsifiers
US6706193B1 (en) * 1999-07-17 2004-03-16 3M Innovative Properties Company Method for recovering fluorinated emulsifiers from aqueous phases
US6255536B1 (en) * 1999-12-22 2001-07-03 Dyneon Llc Fluorine containing vinyl ethers
US6593416B2 (en) * 2000-02-01 2003-07-15 3M Innovative Properties Company Fluoropolymers
US6512089B1 (en) * 2000-02-01 2003-01-28 3M Innovative Properties Company Process for working up aqueous dispersions of fluoropolymers
US6576703B2 (en) * 2000-02-22 2003-06-10 Ausimont S.P.A. Process for the preparation of aqueous dispersions of fluoropolymers
US20040010156A1 (en) * 2000-08-11 2004-01-15 Masahiro Kondo Method of separating anionic fluorochemical surfactant
US7045591B2 (en) * 2000-08-30 2006-05-16 Hoffmann-La Roche Inc. Selective cyclic peptides with melanocortin-4 receptor (MC4-R) agonist activity
US6774164B2 (en) * 2000-09-22 2004-08-10 Dupont Dow Elastomers L.L.C. Process for producing fluoroelastomers with fluorinated anionic surfactants
US20020040119A1 (en) * 2000-10-04 2002-04-04 Tang Phan L. Process for producing fluoroelastomers
US6512063B2 (en) * 2000-10-04 2003-01-28 Dupont Dow Elastomers L.L.C. Process for producing fluoroelastomers
US20020114421A1 (en) * 2001-01-31 2002-08-22 Erbes John G. Jet pump beam lock
US6720437B2 (en) * 2001-02-07 2004-04-13 E. I. Du Pont De Nemours And Company Fluorinated carboxylic acid recovery and reuse
US6715877B2 (en) * 2001-03-10 2004-04-06 Vasyl Molebny Method of measurement of wave aberrations of an eye and device for performing the same
US20040072977A1 (en) * 2001-03-26 2004-04-15 Ralph Kaulbach Aqueous emulsion polymerization process for producing fluoropolymers
US6703520B2 (en) * 2001-04-24 2004-03-09 3M Innovative Properties Company Process of preparing halogenated esters
US6861490B2 (en) * 2001-05-02 2005-03-01 3M Innovative Properties Company Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers
US20030018148A1 (en) * 2001-05-02 2003-01-23 3M Innovative Properties Company Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers
US6750304B2 (en) * 2001-05-02 2004-06-15 3M Innovative Properties Company Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers
US20040132939A1 (en) * 2001-05-02 2004-07-08 Harald Kaspar Emulsifier free aqueous emulsion polumerization process for making fluoropolymers
US7074862B2 (en) * 2001-05-02 2006-07-11 3M Innovative Properties Company Emulsifier free aqueous emulsion polymerization process for making fluoropolymers
US6693152B2 (en) * 2001-05-02 2004-02-17 3M Innovative Properties Company Emulsifier free aqueous emulsion polymerization process for making fluoropolymers
US7045571B2 (en) * 2001-05-21 2006-05-16 3M Innovative Properties Company Emulsion polymerization of fluorinated monomers
US20060160947A1 (en) * 2001-05-21 2006-07-20 3M Innovative Properties Company Emulsion Polymerization of Fluorinated Monomers
US6878772B2 (en) * 2002-02-12 2005-04-12 Solvay Solexis S.P.A. Fluoropolymer aqueous dispersions
US20030153674A1 (en) * 2002-02-12 2003-08-14 Solvay Solexis S.P.A Fluoropolymer aqueous dispersions
US20050038177A1 (en) * 2002-03-20 2005-02-17 Asahi Glass Company Limited Aqueous polytetrafluoroethylene dispersion composition and process for its production
US20050070633A1 (en) * 2002-05-22 2005-03-31 3M Innovative Properties Company Process for reducing the amount of fluorinated surfactant in aqueous fluoropolymer dispersions
US20050150833A1 (en) * 2002-06-19 2005-07-14 Asahi Glass Company Limited Method for recovering fluorine-containing emulsifier
US20050171381A1 (en) * 2002-09-30 2005-08-04 Daikin Industries, Ltd. Process for preparing fluorocarboxylic acids
US20040087703A1 (en) * 2002-10-31 2004-05-06 3M Innovative Properties Company Emulsifier free aqueous emulsion polymerization to produce copolymers of a fluorinated olefin and hydrocarbon olefin
US20060041051A1 (en) * 2002-11-29 2006-02-23 Yasukazu Nakatani Method for purification of aqueous fluoropolymer emulsions, purified emulsions, and fluorine-containing finished articles
US20040116742A1 (en) * 2002-12-17 2004-06-17 3M Innovative Properties Company Selective reaction of hexafluoropropylene oxide with perfluoroacyl fluorides
US20050043471A1 (en) * 2003-01-22 2005-02-24 3M Innovative Properties Company Aqueous fluoropolymer dispersion comprising a melt processible fluoropolymer and having a reduced amount of fluorinated surfactant
US20040143052A1 (en) * 2003-01-22 2004-07-22 3M Innovative Properties Company Aqueous fluoropolymer dispersion comprising a melt processible fluoropolymer and having a reduced amount of fluorinated surfactant
US6861466B2 (en) * 2003-02-28 2005-03-01 3M Innovative Properties Company Fluoropolymer dispersion containing no or little low molecular weight fluorinated surfactant
US20050000904A1 (en) * 2003-07-02 2005-01-06 Remi Le Bec Process for the recovery of fluorosurfactants by active charcoal
US20050090613A1 (en) * 2003-10-22 2005-04-28 Daikin Industries, Ltd. Process for preparing fluorine-containing polymer latex
US20050090601A1 (en) * 2003-10-24 2005-04-28 3M Innovative Properties Company Aqueous dispersions of polytetrafluoroethylene particles
US20070135558A1 (en) * 2003-10-31 2007-06-14 Nobuhiko Tsuda Process for producing aqueous fluoropolymer dispersion and aqueous fluoropolymer dispersion
US20050154104A1 (en) * 2003-12-04 2005-07-14 Solvay Solexis S.P.A. TFE copolymers
US20070155891A1 (en) * 2003-12-09 2007-07-05 Daikin Industries, Ltd. Water base dispersion of fluorinated polymer and process for producing the same
US20070149733A1 (en) * 2003-12-25 2007-06-28 Masao Otsuka Process for preparing fluoropolymer
US7018541B2 (en) * 2004-02-05 2006-03-28 3M Innovative Properties Company Removal of fluorinated surfactants from waste water
US20050177000A1 (en) * 2004-02-05 2005-08-11 3M Innovative Properties Company Method of recovering fluorinated acid surfactants from adsorbent particles loaded therewith
US20050173347A1 (en) * 2004-02-05 2005-08-11 3M Innovative Properties Company Removal of fluorinated surfactants from waste water
US20070117915A1 (en) * 2004-07-28 2007-05-24 Asahi Glass Company, Limited Fluoropolymer latex, process for its production, and fluoropolymer
US20070015937A1 (en) * 2005-07-15 2007-01-18 3M Innovative Properties Company Process for recovery of fluorinated carboxylic acid surfactants from exhaust gas
US20070027251A1 (en) * 2005-07-15 2007-02-01 3M Innovative Properties Company Method of removing fluorinated carboxylic acid from aqueous liquid

Cited By (112)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8598267B2 (en) 2001-09-05 2013-12-03 3M Innovative Properties Company Fluoropolymer dispersion containing no or little low molecular weight fluorinated surfactant
US20080287599A1 (en) * 2001-09-05 2008-11-20 3M Innovative Properties Company Fluoropolymer dispersion containing no or little low molecular weight fluorinated surfactant
US20050192397A1 (en) * 2004-03-01 2005-09-01 3M Innovative Properties Company Method of coating a substrate with a fluoropolymer dispersion
US20060199898A1 (en) * 2005-03-04 2006-09-07 Asahi Glass Company, Limited Fluorinated elastomer latex, its production method, fluorinated elastomer and fluororubber molded product
US7812086B2 (en) 2005-03-04 2010-10-12 Asahi Glass Company, Limited Fluorinated elastomer latex, its production method, fluorinated elastomer and fluororubber molded product
US8614265B2 (en) 2005-07-15 2013-12-24 3M Innovative Properties Company Method of making fluoropolymer dispersion
US7776946B2 (en) 2005-07-15 2010-08-17 3M Innovative Properties Company Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
US20070015866A1 (en) * 2005-07-15 2007-01-18 3M Innovative Properties Company Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
US7671112B2 (en) 2005-07-15 2010-03-02 3M Innovative Properties Company Method of making fluoropolymer dispersion
US8222322B2 (en) 2005-07-15 2012-07-17 3M Innovative Properties Company Method of making fluoropolymer dispersion
US20070015864A1 (en) * 2005-07-15 2007-01-18 3M Innovative Properties Company Method of making fluoropolymer dispersion
US20100113679A1 (en) * 2005-07-15 2010-05-06 3M Innovative Properties Company Method of making fluoropolymer dispersion
US20070015937A1 (en) * 2005-07-15 2007-01-18 3M Innovative Properties Company Process for recovery of fluorinated carboxylic acid surfactants from exhaust gas
US8404790B2 (en) 2005-07-15 2013-03-26 3M Innovative Properties Company Aqueous emulsion polymerization process for producing fluoropolymers
US20070015865A1 (en) * 2005-07-15 2007-01-18 3M Innovative Properties Company Aqueous emulsion polymerization of fluorinated monomers using a perfluoropolyether surfactant
US20080182913A1 (en) * 2005-10-14 2008-07-31 Asahi Glass Company, Limited Method for regenerating basic anion-exchange resin
US7622608B2 (en) * 2005-10-14 2009-11-24 Asahi Glass Company, Limited Method for regenerating basic anion-exchange resin
US20080200571A1 (en) * 2005-10-17 2008-08-21 Asahi Glass Company, Limited Aqueous polytetrafluoroethylene emulsion, polytetrafluoroethylene fine powder and porous material obtained therefrom
US7851573B2 (en) 2005-10-17 2010-12-14 Asahi Glass Company, Limited Aqueous polytetrafluoroethylene emulsion, polytetrafluoroethylene fine powder and porous material obtained therefrom
US7855259B2 (en) 2005-10-20 2010-12-21 Asahi Glass Company, Limited Method for producing melt-processable fluororesin
US7709566B2 (en) 2005-10-20 2010-05-04 Asahi Glass Company, Limited Polytetrafluoroethylene aqueous dispersion and its product
US20080214714A1 (en) * 2005-10-20 2008-09-04 Asahi Glass Company, Limited Polytetrafluoroethylene aqueous dispersion and its product
US20080207859A1 (en) * 2005-10-26 2008-08-28 Asahi Glass Company, Limited Fluororesin having low residual amount of fluorinated emulsifier and process for its production
US7659333B2 (en) * 2005-11-24 2010-02-09 3M Innovative Properties Company Fluorinated surfactants for use in making a fluoropolymer
US20070117914A1 (en) * 2005-11-24 2007-05-24 3M Innovative Properties Company Fluorinated surfactants for use in making a fluoropolymer
US7838608B2 (en) 2005-12-21 2010-11-23 3M Innovative Properties Company Fluorinated surfactants for making fluoropolymers
US20070142541A1 (en) * 2005-12-21 2007-06-21 3M Innovative Properties Company Fluorinated surfactants for making fluoropolymers
US20110034604A1 (en) * 2005-12-21 2011-02-10 3M Innovative Properties Company Fluorinated surfactants for making fluoropolymers
US8859645B2 (en) 2006-04-11 2014-10-14 Solvay Solexis S.P.A. Fluoropolymer dispersion purification
US20090272944A1 (en) * 2006-04-11 2009-11-05 Solvay Solexis S.P.A. Fluoropolymer Dispersion Purification
US20070276103A1 (en) * 2006-05-25 2007-11-29 3M Innovative Properties Company Fluorinated Surfactants
US20070276068A1 (en) * 2006-05-25 2007-11-29 3M Innovative Properties Company Coating composition
US7754795B2 (en) 2006-05-25 2010-07-13 3M Innovative Properties Company Coating composition
US20080015319A1 (en) * 2006-07-13 2008-01-17 Klaus Hintzer Explosion taming surfactants for the production of perfluoropolymers
US20080015304A1 (en) * 2006-07-13 2008-01-17 Klaus Hintzer Aqueous emulsion polymerization process for producing fluoropolymers
US8119750B2 (en) 2006-07-13 2012-02-21 3M Innovative Properties Company Explosion taming surfactants for the production of perfluoropolymers
US20090163653A1 (en) * 2006-08-31 2009-06-25 Asahi Glass Company, Limited Perfluorocarboxylic acid salt and process for producing it
US20100084343A1 (en) * 2007-02-16 2010-04-08 Mader Brian T System and process for the removal of fluorochemicals from water
US20100029878A1 (en) * 2007-04-13 2010-02-04 Asahi Glass Company Limited Method for producing fluoropolymer using fluorocarboxylic acid compound
US20090073118A1 (en) * 2007-04-17 2009-03-19 Sony (China) Limited Electronic apparatus with display screen
US20100305262A1 (en) * 2007-10-12 2010-12-02 Klaus Hintzer Process for manufacturing clean fluoropolymers
US9416251B2 (en) 2007-10-12 2016-08-16 3M Innovative Properties Company Article prepared from clean fluoropolymers
US8541499B2 (en) 2007-10-12 2013-09-24 3M Innovative Properties Company Process for manufacturing clean fluoropolymers
US8466210B2 (en) 2007-12-18 2013-06-18 3M Innovative Properties Company Dental composition containing a surfactant and an F-containing compound, process of production and use thereof
US20090281261A1 (en) * 2008-05-09 2009-11-12 E. I. Du Pont De Nemours And Company Abatement of Fluoroether Carboxylic Acids or Salts Employed in Fluoropolymer Resin Manufacture
US20110082272A1 (en) * 2008-06-24 2011-04-07 Asahi Glass Company, Limited Method for purifying fluorinated compound
US8444857B2 (en) 2008-06-24 2013-05-21 Asahi Glass Company, Limited Method for purifying fluorinated compound
US20110160415A1 (en) * 2008-07-08 2011-06-30 Solvay Solexis S.P.A. Method for manufacturing fluoropolymers
US8703889B2 (en) 2008-07-08 2014-04-22 Solvay Solexis S.P.A. Method for manufacturing fluoropolymers
US9776983B2 (en) 2008-07-08 2017-10-03 Solvay Solexis S.P.A. Method for manufacturing fluoropolymers
US20100113691A1 (en) * 2008-11-06 2010-05-06 E. I. Du Pont De Nemours And Company Fluoro olefin polymerization
US8633328B2 (en) 2008-12-19 2014-01-21 3M Innovative Properties Company Method of making fluorinated alkoxy carboxylic acids and precursors thereof
WO2010071730A1 (en) * 2008-12-19 2010-06-24 3M Innovative Properties Company Method of making fluorinated alkoxy carboxylic acids and precursors thereof
CN102272087A (en) * 2008-12-19 2011-12-07 3M创新有限公司 Method of making fluorinated alkoxy carboxylic acids and precursors thereof
US8440858B2 (en) 2008-12-19 2013-05-14 3M Innovative Properties Company Method of making fluorinated alkoxy carboxylic acids and precursors thereof
US8329813B2 (en) 2009-05-08 2012-12-11 E I Du Pont De Nemours And Company Thermal reduction of fluoroether carboxylic acids or salts from fluoropolymer dispersions
WO2010147817A1 (en) 2009-06-15 2010-12-23 3M Innovative Properties Company Polyether group containing dental composition containing an f-containing compound, process of production and use thereof
WO2011066156A1 (en) 2009-11-26 2011-06-03 3M Innovative Properties Company Method of preparing highly fluorinated carboxylic acids and their salts
US11072671B2 (en) 2010-04-28 2021-07-27 3M Innovative Properties Company Process for producing PTFE and articles thereof
WO2012088258A1 (en) 2010-12-23 2012-06-28 3M Innovative Properties Company Fluoropolymer compositions and purification methods thereof
US9809658B2 (en) 2010-12-23 2017-11-07 3M Innovative Properties Company Fluoropolymer compositions and purification methods thereof
US9453086B2 (en) 2010-12-23 2016-09-27 3M Innovative Properties Company Fluoropolymer compositions and purification methods thereof
WO2012160135A1 (en) 2011-05-26 2012-11-29 Solvay Specialty Polymers Italy S.P.A. Hydro-fluorocompounds
WO2014130603A1 (en) 2013-02-25 2014-08-28 3M Innovative Properties Company Stabilized dental impression composition, kit of parts and use thereof
US9549881B2 (en) 2013-02-25 2017-01-24 3M Innovative Properties Company Stabilized dental impression composition, kit of parts and use thereof
US20170028370A1 (en) * 2014-04-18 2017-02-02 3M Innovative Properties Company Recovery of branched fluorinated emulsifiers
US9694333B2 (en) * 2014-04-18 2017-07-04 3M Innovative Properties Company Recovery of branched fluorinated emulsifiers
CN106232231A (en) * 2014-04-18 2016-12-14 3M创新有限公司 The recovery of branched fluorinated emulsifying agent
WO2015160926A1 (en) * 2014-04-18 2015-10-22 3M Innovative Properties Company Recovery of branched fluorinated emulsifiers
WO2015173194A1 (en) 2014-05-12 2015-11-19 Solvay Specialty Polymers Italy S.P.A. Fluoroelastomers
US10377843B2 (en) 2014-05-12 2019-08-13 Solvay Specialty Polymers Italy S.P.A. Method for the controlled polymerization of fluoromonomers
WO2017102820A1 (en) 2015-12-14 2017-06-22 Solvay Specialty Polymers Italy S.P.A. Method of manufacturing fluoroelastomers
US10882935B2 (en) 2015-12-14 2021-01-05 Solvay Specialty Polymers Italy S.P.A. Method of manufacturing fluoroelastomers
US10744497B2 (en) * 2016-03-04 2020-08-18 3M Innovative Properties Company Method for removing perfluorinated alkanoic acids
US20190070599A1 (en) * 2016-03-04 2019-03-07 3M Innovative Properties Company Method for removing perfluorinated alkanoic acids
EP3375798A1 (en) 2017-03-17 2018-09-19 Solvay Specialty Polymers Italy S.p.A. Method for making fluoropolymers
US11591430B2 (en) 2017-03-17 2023-02-28 Solvay Specialty Polymers Italy S.P.A. Method for making fluoropolymers
WO2018167189A1 (en) 2017-03-17 2018-09-20 Solvay Specialty Polymers Italy S.P.A. Method for making fluoropolymers
WO2018167190A1 (en) 2017-03-17 2018-09-20 Solvay Specialty Polymers Italy S.P.A. Method for making fluoropolymers
WO2018181898A1 (en) 2017-03-31 2018-10-04 ダイキン工業株式会社 Production method for fluoropolymer, surfactant for polymerization, and use of surfactant
EP4257638A2 (en) 2017-03-31 2023-10-11 Daikin Industries, Ltd. Production method for fluoropolymer, surfactant for polymerization, and use of surfactant
WO2018181904A1 (en) 2017-03-31 2018-10-04 ダイキン工業株式会社 Production method for fluoropolymer, surfactant for polymerization, and use of surfactant
EP3858871A1 (en) 2017-03-31 2021-08-04 Daikin Industries, Ltd. Composition comprising a fluoropolymer
WO2019048394A1 (en) 2017-09-08 2019-03-14 Solvay Specialty Polymers Italy S.P.A. Method for making fluoropolymers
US11401352B2 (en) 2017-09-08 2022-08-02 Solvay Specialty Polymers Italy S.P.A. Method for making fluoropolymers
WO2019156175A1 (en) 2018-02-08 2019-08-15 ダイキン工業株式会社 Method for manufacturing fluoropolymer, surfactant for polymerization, use for surfactant, and composition
WO2019168183A1 (en) 2018-03-01 2019-09-06 ダイキン工業株式会社 Method for manufacturing fluoropolymer
EP4317214A2 (en) 2018-03-01 2024-02-07 Daikin Industries, Ltd. Method for manufacturing fluoropolymer
WO2019172382A1 (en) 2018-03-07 2019-09-12 ダイキン工業株式会社 Method for producing fluoropolymer
WO2020104889A1 (en) 2018-11-20 2020-05-28 3M Innovative Properties Company Curable composition containing a polyether-modified polydimethyl siloxane
WO2020213691A1 (en) 2019-04-16 2020-10-22 ダイキン工業株式会社 Method for producing fluoropolymer powder
WO2020218618A1 (en) 2019-04-26 2020-10-29 ダイキン工業株式会社 Process for producing aqueous fluoropolymer dispersion
WO2020250129A1 (en) 2019-06-12 2020-12-17 3M Innovative Properties Company Process of taking a dental impression with a radiation-curable composition containing mercapto-functional polyorganosiloxanes and vqm resins
WO2021015291A1 (en) 2019-07-23 2021-01-28 ダイキン工業株式会社 Method for producing fluoropolymer, polytetrafluoroethylene composition, and polytetrafluoroethylene powder
WO2021045165A1 (en) 2019-09-05 2021-03-11 ダイキン工業株式会社 Method for producing perfluoroelastomer and composition
WO2021100835A1 (en) 2019-11-19 2021-05-27 ダイキン工業株式会社 Method for producing fluoropolymer
EP3945075A1 (en) 2020-07-30 2022-02-02 3M Innovative Properties Company Process for removal of fluoroorganic compounds from emulsions
WO2022024081A1 (en) 2020-07-30 2022-02-03 3M Innovative Properties Company Process for removal of fluoroorganic compounds from emulsions
WO2022024082A1 (en) 2020-07-30 2022-02-03 3M Innovative Properties Company Process to reduce the concentration of fluoroorganic acidic compounds in aqueous dispersions
EP3945074A1 (en) 2020-07-30 2022-02-02 3M Innovative Properties Company Process to reduce the concentration of fluoroorganic acidic compound in aqueous dispersions
EP3945099A1 (en) 2020-07-30 2022-02-02 3M Innovative Properties Company Process for removal of fluoroorganic compounds from aqueous media
WO2022107890A1 (en) 2020-11-19 2022-05-27 ダイキン工業株式会社 Method for manufacturing perfluoroelastomer aqueous dispersion, composition, crosslinkable composition, and crosslinked product
WO2022107891A1 (en) 2020-11-19 2022-05-27 ダイキン工業株式会社 Method for producing fluorine-containing elastomer aqueous dispersion, and composition
WO2022196804A1 (en) 2021-03-18 2022-09-22 ダイキン工業株式会社 Method for producing fluororesin, fluororesin, and aqueous dispersion liquid
WO2022244784A1 (en) 2021-05-19 2022-11-24 ダイキン工業株式会社 Method for producing fluoropolymer, method for producing polytetrafluoroethylene, and composition
WO2022248954A1 (en) 2021-05-26 2022-12-01 3M Innovative Properties Company Dental composition comprising an isorbide component
WO2022260139A1 (en) 2021-06-11 2022-12-15 ダイキン工業株式会社 Production method for aqueous fluorine-containing elastomer dispersion, composition, and aqueous dispersion
WO2023277139A1 (en) 2021-06-30 2023-01-05 ダイキン工業株式会社 Method for producing fluoropolymer composition, and fluoropolymer composition
WO2023277140A1 (en) 2021-06-30 2023-01-05 ダイキン工業株式会社 Method for producing high-purity fluoropolymer-containing composition, and high-purity fluoropolymer-containing composition
EP4219412A1 (en) 2022-01-27 2023-08-02 3M Innovative Properties Company Closed-loop technologies for purifying fluorine containing water streams
WO2023144756A1 (en) 2022-01-27 2023-08-03 3M Innovative Properties Company Closed-loop technologies for purifying fluorine containing water streams
WO2023165912A1 (en) 2022-03-01 2023-09-07 Solvay Specialty Polymers Italy S.P.A. Method for making fluoropolymers containing ion exchange groups

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US8222322B2 (en) 2012-07-17
US20070027251A1 (en) 2007-02-01
US8614265B2 (en) 2013-12-24
US7795332B2 (en) 2010-09-14
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US20120252949A1 (en) 2012-10-04
US7671112B2 (en) 2010-03-02

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