WO2005113644A1 - Fluorinated polyether polyamine and method of making the same - Google Patents

Fluorinated polyether polyamine and method of making the same Download PDF

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Publication number
WO2005113644A1
WO2005113644A1 PCT/US2005/010907 US2005010907W WO2005113644A1 WO 2005113644 A1 WO2005113644 A1 WO 2005113644A1 US 2005010907 W US2005010907 W US 2005010907W WO 2005113644 A1 WO2005113644 A1 WO 2005113644A1
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Prior art keywords
carbon atoms
independently represents
dispersion
composition
group
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PCT/US2005/010907
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English (en)
French (fr)
Inventor
Zai-Ming Qiu
Naiyong Jing
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to DE602005024251T priority Critical patent/DE602005024251D1/de
Priority to AT05730920T priority patent/ATE485330T1/de
Priority to EP05730920A priority patent/EP1742987B1/en
Priority to JP2007511370A priority patent/JP5065011B2/ja
Publication of WO2005113644A1 publication Critical patent/WO2005113644A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain

Definitions

  • Fluorinated polyethers have useful properties that include low refractive index, soil resistance, lubricity, and high water repellency. Accordingly, fluorinated polyethers have been incorporated into various protective coatings to provide one or more of low refractive index, cleanability, durability, and scratch resistance. However, fluorinated polyethers typically are only soluble or dispersible in organic solvents, and in particular in costly fluorinated organic solvents. Further, if such solutions or dispersions containing volatile organic solvent are coated on a substrate. Given the recent trend in industry to remove volatile organic solvent from chemical formulations, there remains a continuing need for fluorinated polyether materials that are soluble or dispersible in solvents other than organic solvents.
  • the present invention provides a composition comprising at least one compound described by the formula X 1 (NR 1 R 2 ) n X 2 or an acid salt thereof, wherein ⁇ l represents H, an alkyl group having from 1 to 8 carbon atoms, or an aryl group having from 6 to 10 carbon atoms; and ⁇ 2 represents -NR ⁇ H; each R!
  • each R 2 independently represents an alkylene group having from 2 to 8 carbon atoms
  • Z represents O F(RfO) x QC— or each Rf independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms
  • each Q independently represents -CF 2 -, -CF(CF 3 )-, -CF 2 CF 2 -, -CF 2 CF 2 CF 2 -, -CF 2 CF(CF 3 )-, -CF(CF 3 )CF 2 -, -CF 2 CF 2 CH 2 -, -CF 2 CH 2 -, or -CF(CF 3 )CH 2 -
  • n and x independently represent integers greater than 2, wherein the composition has at least three Z groups, and wherein the number of primary and secondary amino
  • each Rf independently represents a fluorinated alkylene group having from 1 to 8 carbon atoms; R3 represents alkoxy having from 1 to 8 carbon atoms, fluorine, or chlorine; each x independently represents an integer greater than or equal to 2; each Q independently represents -CF 2 -, -CF(CF 3 )-, -CF 2 CF 2 -, -CF 2 CH 2 -, -CF 2 CF 2 CF 2 -, -CF 2 CF(CF 3 )-, -CF(CF 3 )CF 2 -, -CF 2 CF 2 CH 2 -, or -CF(CF 3 )CH 2 -; (b) providing at least one polyamine described by the formula wherein ⁇ l represents H, an alkyl group having from 1 to 8 carbon atoms, or an aryl group having from 6 to 10 carbon atoms; X 2 represents -NR 1 !!; each R!
  • each R 2 independently represents an alkylene group having from 2 to 8 carbon atoms
  • Z represents O F(Rf ) x QC- or each Rf independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms
  • each Q independently represents -CF 2 -, -CF(CF 3 )-, -CF 2 CF 2 -, -CF 2 CF 2 CF 2 -, -CF 2 CF(CF 3 )-, -CF(CF 3 )CF 2 -, -CF 2 CF 2 CH 2 -, -CF 2 CH 2 -, or -CF(CF 3 )CH 2 -
  • each n and x independently represent integers greater than 2, wherein the polyamine has at combined total of at least three primary and secondary amino groups; and (c) combining the reactive fluorinated polyether and the
  • compositions according to the present invention are typically dispersible in aqueous media, and are versatile synthetic intermediates for a wide variety of polymerizable derivatives.
  • the present invention provides a dispersion having a continuous aqueous phase, the dispersion comprising at least one compound described by the formula X ⁇ NRiR 2 ) ⁇ 2 or an acid salt thereof, wherein ⁇ l represents H, an alkyl group having from 1 to 8 carbon atoms, or an aryl group having from 6 to 10 carbon atoms; and X 2 represents -NR 1 !!; each R!
  • each R 2 independently represents an alkylene group having from 2 to 8 carbon atoms
  • Z represents O F(RfO) x QC— or each Rf independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms
  • each Q independently represents -CF 2 -, -CF(CF 3 )-, -CF 2 CF 2 -, -CF 2 CF 2 CF 2 -, -CF 2 CF(CF 3 )-, -CF(CF 3 )CF 2 -, -CF 2 CF 2 CH 2 -, -CF 2 CH 2 -, or -CF(CF 3 )CH 2 -
  • n and x independently represent integers greater than 2, wherein the composition has at least one Z group, and wherein the number of primary
  • the present invention provides a method of making a dispersion comprising: (a) providing at least one reactive fluorinated polyether described by the formula O F(RP) X QC-R 3 or O O * II II 3 R — CQ(Rp) ⁇ QC-R wherein each Rf independently represents a fluorinated alkylene group having from 1 to 8 carbon atoms; R3 represents alkoxy having from 1 to 8 carbon atoms, fluorine, or chlorine; each x independently represents an integer greater than or equal to 2; each Q independently represents -CF 2 -, -CF(CF 3 )-, -CF 2 CF 2 -, -CF 2 CH 2 -, -CF 2 CF 2 CF 2 -, -CF 2 CF(CF 3 )-, -CF(CF 3 )CF 2 -, -CF 2 CF 2 CH 2 -, or -CF(CF 3 )CH 2 -;
  • ⁇ l represents H, an alkyl group having from 1 to 8 carbon atoms, or an aryl group having from 6 to 10 carbon atoms
  • X 2 represents -NRlH
  • each R1 independently represents H, an alkyl group having from 1 to 8 carbon atoms, or a hydroxyalkyl group having from 2 to 8 carbon atoms, or Z
  • each R 2 independently represents an alkylene group having from 2 to 8 carbon atoms
  • Z represents O F(RfO) x QC— or O O II II 1 2 2
  • each Rf independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms
  • each Q independently represents -CF 2 -, -CF(CF 3 ) ⁇ , -CF 2 CF 2 -, -CF 2 CF 2 CF 2 -, -CF 2 CF(CF 3 )-, -CF(CF 3 )CF 2 -, -CF 2 CF 2 CH 2 -,
  • compositions that may be prepared according to a method in which at least one amine-reactive fluorinated polyether acid derivative such as, for example, esters (for example, alkyl esters having from 1 to 8 carbon atoms) and acid halides (for example, acid fluoride or acid chloride) is condensed with a primary and/or secondary amine.
  • amine-reactive fluorinated polyether acid derivatives are described by the formula O F(Rf ) x QC-R 3 or Each Rf independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms.
  • Rf may be a partially fluorinated group such as -
  • CF2CF2CH2-, -CH2CF2CH2-, or a perfluorinated alkylene group having from 1 to 6 carbon atoms such as -CF 2 -, -CF(CF3)-, -CF2CF2-, -CF2CF2CF2-, -CF(CF3)CF 2 -,
  • -CF2CF(CF3)- -(CF2)5-, or -(CF2)6-. Since each Rf is independently selected, -(RfO) x - may thus represent, for example, -(CF(CF3)CF2 ⁇ )g-, -(CF2CF2 ⁇ )3(CF(CF3)CF2 ⁇ ) ⁇ 2-,
  • n + m is in a range of from 6 up to 12.
  • Each x independently represents an integer greater than or equal to 2.
  • x may be greater than 3 or greater than 4.
  • R3 represents an alkoxy group having from 1 to 8 carbon atoms, fluorine, or chlorine.
  • R ⁇ may be methoxy, ethoxy, isopropoxy, or butoxy.
  • R ⁇ may be may be linear, cyclic, and/or branched. Methods for making such fluorinated polyethers having an amine-reactive end group are well known. Further details procedures for the preparation of such compounds can be found in, for example, U.S. Pat. Nos.
  • fluorinated polyethers having an amine-reactive end group are generally available in a range of molecule weights range, in some applications it may be desirable that the number average molecular weight of the fluorinated polyethers be at least 1,000 g/mole, although this is not a requirement.
  • the amine-reactive fluorinated polyether acid derivative is combined with a polyamine having a combined total of at least 3 (for example, 4, 5, 6, 10, 20, 50, 100, or even more) primary and secondary amine nitrogen atoms to form an amide condensate.
  • the molar ratio of amine-reactive fluorinated polyether acid derivatives to amine, which are combined to form aqueous dispersions of the present invention may have any ratio greater than zero.
  • the molar ratio of amine-reactive fluorinated polyether acid derivatives that may be used if forming amide condensates in forms other than as an aqueous dispersion is at least 3 (for example, 3:1, 4:1, 5:1, 10:1, 20:1, up to 50:1, or more). Higher molar ratios are typically desirable for applications in which low energy substrates are to be coated with the composition, while low ratios are typically desirable if water dispersibility is desired.
  • Two or more amide condensates may be blended, for example, as in the case of statistical mixtures (for example, 2.5:1 condensate), although it will be recognized that the mixture will comprise some material having a molar ratio of at least 3:1.
  • the stoichiometry of addition of the amine-reactive fluorinated polyether acid derivative to polyamine may be selected such that the resultant amide condensate has at least one or even at least two primary and/or secondary amino groups, for example, which may be used to covalently attach additional functionality to the amide condensate.
  • primary amino groups are more reactive to the amine-reactive fluorinated polyether acid derivative than secondary amino groups. It is typically possible therefore to control the condensation conditions in order to cause preferential reaction with primary amino groups in preference to secondary groups.
  • a reaction temperature in a range of from 50 °C up to 80
  • °C typically results in amide condensates with primary amino groups, but not with secondary amino groups that typically need a higher temperature (for example, 100-120 oC) to form.
  • some or all of the amino groups of the polyamine may be deactivated by reaction with an amine reactive group (for example, an acid derivative such as an ester, alkyl carbonate, or acid halide), and in a second step a fluorinated polyether can be reacted with remaining amino groups (for example, primary and/or secondary amino groups) of the polyamine.
  • an amine reactive group for example, an acid derivative such as an ester, alkyl carbonate, or acid halide
  • deactivation or primary amines may accomplished using one or more amine-protecting groups (that is, blocking groups) that can be later removed, for example, after reaction of one or more secondary amino groups with an amine-reactive fluorinated polyether acid derivative.
  • amine-protecting groups that is, blocking groups
  • Useful amine- protecting groups and methods for their use and removal are well known in the chemical arts.
  • ⁇ l represents H, an alkyl group having from 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, hexyl, isooctyl), an aryl group having from 6 to 10 carbon atoms (for example, phenyl, chlorophenyl, naphthyl), an alkaryl group having from 7 to 15 carbon atoms (for example, 4-tolyl, 2-methylphenyl, 2,4-dimethylphenyl, octylphenyl), or an aralkyl group having from 7 to 15 carbon atoms (for example, phenylethyl, 2- chlorophenylhexyl, (2',4'-dimethylphenyl)propyl, phenylnonyl).
  • ⁇ l represents H, an alkyl group having from 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, hexyl, isooc
  • ⁇ l may be linear, cyclic, and/or branched.
  • X 2 represents -NR1H.
  • R! represents H, an alkyl group having from 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, hexyl, isooctyl), an aminoalkyl group having from 2 to 8 carbon atoms, or a hydroxyalkyl group having from 2 to 8 carbon atoms.
  • R* may be may be linear, cyclic, and/or branched.
  • Each R 2 independently represents an alkylene group having from 2 to 8 carbon atoms (for example, ethylene, propylene, hexylene).
  • R 2 may be may be linear, cyclic, and/or branched.
  • n an integer greater than 2 (for example, 3, 4, 5, 15, 50, 100 or more).
  • useful polyamines include polyamines having at least three amino groups, wherein the three amino groups are primary, secondary, or a combination thereof. Examples include H 2 N(CH2CH2NH)2H, H 2 N(CH2CH 2 NH)3H, H2N(CH 2 CH 2 NH)4H,
  • H2N(CH2)3NHCH2CH CHCH2NH(CH2)3NH2, H2N(CH2)4NH(CH2)3NH 2)
  • compositions according to the present invention are dispersible or soluble organic solvent and/or water.
  • compositions according to the present invention may comprise at least 5, 10, or 20 percent by weight up to 30 percent or more of an aqueous dispersion or solution, enabling, for example, formulation of water-based, solvent-free formulations of the compositions.
  • dispersibility and solubility depend at least in part on the ratio of primary, secondary, and quaternary amine groups to fluorinated polyether group(s) in the composition, with higher ratios favoring dispersibility and/or solubility.
  • Compositions according to the present invention whether in purified form or as dispersions, and useful for forming protective and/or lubricious coatings on substrates.
  • compositions of the present invention may exist in free base form or as an acid salt (for example, the salt of the free base form of the composition and a Bronsted acid such as sulfuric acid, nitric acid, hydrochloric acid acetic acid).
  • a Bronsted acid such as sulfuric acid, nitric acid, hydrochloric acid acetic acid.
  • mm millimeters
  • g grams
  • mg milligrams
  • mol mole
  • mmol millimole
  • meq milliequivalents
  • mL milliliters
  • C ⁇ phenyl
  • EXAMPLE 1 This example describes the preparation of a 4: 1 molar ratio amide condensate of FC-1 with H 2 N(CH2CH2NH) H.
  • FC-1 200 mmol
  • H2N(CH2CH2NH) 5 H 50 mmol
  • EXAMPLE 2 This example describes the preparation of a 3:1 molar ratio amide condensate of FC-1 with H 2 N(CH2CH2NH) 5 H. In a sealed 120 mL glass tube, 10 g (10 mmol) of FC-1 was mixed with 0.77 g of
  • EXAMPLE 3 This example describes the preparation of a 2: 1 molar ratio amide condensate of FC-1 with H2N(CH2CH 2 NH)5H. In a sealed 120 mL glass tube, 20 g (20 mmol) of FC-1 was mixed with 2.32 g of
  • EXAMPLE 4 This example describes the preparation of a 1.5:1 molar ratio amide condensate of FC-1 with H2N(CH2CH2CH 2 NH) 2 H. In a sealed 120 mL glass tube, 15 g (15 mmol) of FC-1 was mixed with 1.31 g of
  • EXAMPLE 5 This example describes the preparation of a 2:1 molar ratio amide condensate of FC-1 with N(CH 2 CH 2 NH2)3. In a sealed 120 mL glass tube, 40 g (40 mmol) of FC-1 was mixed with 2.92 g of
  • EXAMPLE 6 This example describes the preparation of an acid salt of a 2: 1 molar ratio amide condensate of FC-1 with H2N(CH 2 CH 2 NH) 5 H.
  • FC-1 20 mmol
  • H2N(CH2CH2NH)5H 10 mmol
  • EXAMPLE 7 This example describes the preparation of a 2: 1 molar ratio amide condensate of FC-2 to H 2 N(CH2CH 2 NH)5H.
  • a flask was charged with 50 g (41.29 mmol) of FC-2 and 4.80 g (20.64 mmol) of H2N(CH2CH2NH)5H, both at room temperature, resulting in a cloudy solution.
  • the flask was swirled and the temperature of the mixture rose to 45 °C resulting in a water- white liquid, which was heated overnight at 55 °C.
  • EXAMPLE 11 This example describes the preparation of a 8:1 molar ratio amide condensate of FC-2 with -(NHCH2CH2) x (N(CH2CH2NH2)CH 2 CH2)y-.
  • the mixture was heated at 110 °C for two hours to give a clear liquid.
  • Infrared spectroscopic analysis showed that the absorption band at 1787 cm -1 , attributed to the ester carbonyl group of

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyamides (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
PCT/US2005/010907 2004-05-07 2005-03-31 Fluorinated polyether polyamine and method of making the same Ceased WO2005113644A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE602005024251T DE602005024251D1 (de) 2004-05-07 2005-03-31 Fluoriertes polyetherpolyamin und herstellungsverfahren dafür
AT05730920T ATE485330T1 (de) 2004-05-07 2005-03-31 Fluoriertes polyetherpolyamin und herstellungsverfahren dafür
EP05730920A EP1742987B1 (en) 2004-05-07 2005-03-31 Fluorinated polyether polyamine and method of making the same
JP2007511370A JP5065011B2 (ja) 2004-05-07 2005-03-31 フッ素化ポリエーテルポリアミンおよびフッ素化ポリエーテルポリアミンを製造する方法

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US10/840,969 US7288619B2 (en) 2004-05-07 2004-05-07 Fluorinated polyether polyamine and method of making the same
US10/840,969 2004-05-07

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EP (1) EP1742987B1 (https=)
JP (1) JP5065011B2 (https=)
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AT (1) ATE485330T1 (https=)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7342080B2 (en) * 2004-05-07 2008-03-11 3M Innovative Properties Company Polymerizable compositions, methods of making the same, and composite articles therefrom
EP3635022A4 (en) * 2017-05-19 2021-02-24 Etna-Tec, Ltd Process for the preparation of functionalized fluorinated monomers, fluorinated monomers and compositions for the preparation thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2519529B1 (en) * 2009-12-30 2015-10-21 3M Innovative Properties Company Moisture-curable siloxane-containing and fluorocarbon-containing compounds and polymers formed therefrom
CN102770478B (zh) 2009-12-30 2014-03-12 3M创新有限公司 具有全氟聚醚链段和多个氨基乙二酰胺基的共聚物
WO2019241186A1 (en) 2018-06-12 2019-12-19 3M Innovative Properties Company Fluoropolymer coating compositions comprising amine curing agents, coated substrates and related methods
US11866602B2 (en) 2018-06-12 2024-01-09 3M Innovative Properties Company Fluoropolymer compositions comprising fluorinated additives, coated substrates and methods
WO2021088198A1 (en) 2019-11-04 2021-05-14 3M Innovative Properties Company Electronic telecommunications articles comprising crosslinked fluoropolymers and methods
WO2021090111A1 (en) 2019-11-04 2021-05-14 3M Innovative Properties Company Fluoropolymer compositions comprising a curing agent with ethylenically unsaturated and electron donor groups, and substrates coated therewith
US20240218202A1 (en) 2021-05-05 2024-07-04 3M Innovative Properties Company Electronic telecommunications articles and compositions comprising fluorinated curing agents

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3250808A (en) * 1963-10-31 1966-05-10 Du Pont Fluorocarbon ethers derived from hexafluoropropylene epoxide
US5718833A (en) * 1996-01-16 1998-02-17 Nok Corporation Fluorine-based magnetic fluid

Family Cites Families (78)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242218A (en) * 1961-03-29 1966-03-22 Du Pont Process for preparing fluorocarbon polyethers
US3322826A (en) * 1962-04-11 1967-05-30 Du Pont Polymerization of hexafluoropropylene epoxide
US3274239A (en) * 1962-08-31 1966-09-20 Du Pont Fluorocarbon ethers
US3293306A (en) * 1963-06-14 1966-12-20 Du Pont Perfluorinated ether alcohols
US3250807A (en) * 1963-08-23 1966-05-10 Du Pont Dicarboxylic acids of fluorocarbon ethers and fluorides, esters, amides and salts thereof
US3536749A (en) * 1966-06-08 1970-10-27 Minnesota Mining & Mfg Fluorocarbon-acrylate products
US3553179A (en) * 1968-05-06 1971-01-05 Du Pont Acrylate-type esters of perfluoropoly-oxa-alkaneamidoalkyl alcohols and their polymers
US3544537A (en) * 1968-05-31 1970-12-01 Du Pont Poly(perfluoroalkoxy)polyfluoroalkyl acrylate-type esters and their polymers
US4085137A (en) * 1969-03-10 1978-04-18 Minnesota Mining And Manufacturing Company Poly(perfluoroalkylene oxide) derivatives
US4094911A (en) * 1969-03-10 1978-06-13 Minnesota Mining And Manufacturing Company Poly(perfluoroalkylene oxide) derivatives
US3810874A (en) * 1969-03-10 1974-05-14 Minnesota Mining & Mfg Polymers prepared from poly(perfluoro-alkylene oxide) compounds
NL7100763A (https=) * 1970-01-24 1971-07-27
US3864318A (en) * 1970-01-24 1975-02-04 Monteratini Edison S P A Acrylic and methacrylic monomers, polymers and copolymers
US4256560A (en) * 1978-08-28 1981-03-17 Ppg Industries, Inc. Curable resinous compositions useful in coating applications
US4262072A (en) * 1979-06-25 1981-04-14 Minnesota Mining And Manufacturing Company Poly(ethylenically unsaturated alkoxy) heterocyclic protective coatings
US4321404A (en) * 1980-05-20 1982-03-23 Minnesota Mining And Manufacturing Company Compositions for providing abherent coatings
JPS5759843A (en) * 1980-09-30 1982-04-10 Neos Co Ltd Perfluoroalkyl ether amide derivative and its preparation
US4818801A (en) * 1982-01-18 1989-04-04 Minnesota Mining And Manufacturing Company Ophthalmic device comprising a polymer of a telechelic perfluoropolyether
US4440918A (en) * 1982-01-18 1984-04-03 Minnesota Mining And Manufacturing Company Contact lens containing a fluorinated telechelic polyether
US4567073A (en) * 1982-07-02 1986-01-28 Minnesota Mining And Manufacturing Company Composite low surface energy liner of perfluoropolyether
US4472480A (en) * 1982-07-02 1984-09-18 Minnesota Mining And Manufacturing Company Low surface energy liner of perfluoropolyether
JPS6072924A (ja) * 1983-09-30 1985-04-25 Nippon Oil & Fats Co Ltd 塗料
US4647413A (en) * 1983-12-27 1987-03-03 Minnesota Mining And Manufacturing Company Perfluoropolyether oligomers and polymers
US4614667A (en) * 1984-05-21 1986-09-30 Minnesota Mining And Manufacturing Company Composite low surface energy liner of perfluoropolyether
JPS61111308A (ja) 1984-11-06 1986-05-29 Green Cross Corp:The フツ素含有ポリマ−および医療用酸素透過体
US4654233A (en) * 1984-11-21 1987-03-31 Minnesota Mining And Manufacturing Company Radiation-curable thermoplastic coating
EP0186033B1 (en) * 1984-12-12 1992-08-19 Daikin Industries, Limited A material for contact lenses
IT1185520B (it) * 1985-02-22 1987-11-12 Montefluos Spa Poliacrilati e poliacrilammidi fluorurati a grado di reticolazione controllato e loro procedimento di preparazione
IT1201470B (it) * 1985-09-24 1989-02-02 Montefluos Spa Impiego di derivati dei perfluoropolieteri per la protezione dei materiali lapidei dagli agenti atmosferici
IT1213071B (it) * 1986-05-07 1989-12-07 Ausimont Spa Perfluoropolieteri esenti da ossigeno perossidico e contenenti gruppi perfluoroepossidici disposti lungo la catena perfluoropolieterea.
DE3787118T2 (de) * 1986-05-28 1994-01-20 Daikin Ind Ltd Fluor enthaltende, Wasser und Ölabweisende Zubereitung.
KR930001699B1 (ko) * 1986-12-29 1993-03-11 미쯔이세끼유 가가꾸 고오교오 가부시끼가이샤 플루오르 함유 중합체 및 그 중합체로 구성되는 산소투과체
US4830910A (en) * 1987-11-18 1989-05-16 Minnesota Mining And Manufacturing Company Low adhesion compositions of perfluoropolyethers
US4855184A (en) * 1988-02-02 1989-08-08 Minnesota Mining And Manufacturing Company Radiation-curable protective coating composition
AU608420B2 (en) * 1988-03-15 1991-03-28 Minnesota Mining And Manufacturing Company Polymer claddings for optical fibre waveguides
US4873140A (en) * 1988-04-27 1989-10-10 Minnesota Mining And Manufacturing Company Articles having low adhesion articles having coatings thereon
US5076844A (en) * 1988-12-10 1991-12-31 Goldschmidt AG & GDF Gesellschaft fur Dentale Forschung u. Innovationen GmbH Perfluoroalkyl group-containing (meth-)acrylate esters, their synthesis and use in dental technology
US4929692A (en) * 1989-01-11 1990-05-29 Ciba-Geigy Corporation Crosslinked copolymers and ophthalmic devices made from vinylic macromers containing perfluoropolyalkyl ether and polyalkyl ether segments and minor amounts of vinylic comonomers
JPH0339928A (ja) 1989-07-07 1991-02-20 Asahi Chem Ind Co Ltd コンタクトレンズ材料
US4971424A (en) * 1989-10-26 1990-11-20 Minnesota Mining And Manufacturing Co. Radiation curable cladding compositions
AU632869B2 (en) * 1989-12-14 1993-01-14 Minnesota Mining And Manufacturing Company Fluorocarbon-based coating compositions and articles derived therefrom
WO1992015627A1 (en) * 1991-03-06 1992-09-17 Minnesota Mining And Manufacturing Company Polyfluoropolyether graft copolymers
US5484822A (en) * 1991-06-24 1996-01-16 Polaroid Corporation Process and composition for cladding optic fibers
US5239026A (en) * 1991-08-26 1993-08-24 Minnesota Mining And Manufacturing Company Low loss high numerical aperture cladded optical fibers
JP3161552B2 (ja) 1992-01-31 2001-04-25 大日本インキ化学工業株式会社 硬化性組成物及び絶縁電線
JP3395850B2 (ja) 1992-02-27 2003-04-14 大日本インキ化学工業株式会社 光ファイバクラッド材及びそれで被覆された光ファイバ
JPH06211945A (ja) 1993-01-20 1994-08-02 Nissin High Voltage Co Ltd ハードコートシートとその製造方法
IT1270818B (it) 1993-04-28 1997-05-13 Ausimont Spa Coatings a base di perfluoropolieteri contenenti gruppi acrilici
AUPN215995A0 (en) * 1995-04-04 1995-04-27 Ciba-Geigy Ag Novel materials
CA2215139A1 (en) * 1995-04-04 1996-10-10 Commonwealth Scientific And Industrial Research Organisation Polymerizable perfluoroalkylether macromer
IT1273609B (it) * 1995-04-28 1997-07-08 Ausimont Spa Procedimento per la protezione delle superfici lapidee o di rivestimento
JP3463070B2 (ja) * 1996-01-16 2003-11-05 Ｎｏｋ株式会社 フッ素ベース磁性流体
US6184339B1 (en) * 1996-11-14 2001-02-06 The United States Of America As Represented By The Secretary Of The Commerce High strength polymeric networks derived from (meth) acrylate resins with organofluorine content and process for preparing same
US5822489A (en) * 1996-12-31 1998-10-13 Lucent Technologies, Inc. Low refractive index photo-curable composition for waveguide applications
IT1290462B1 (it) * 1997-04-08 1998-12-03 Ausimont Spa Polimeri idrogenati modificati
US6383633B1 (en) * 1997-05-14 2002-05-07 3M Innovative Properties Company Fluorochemical composition comprising a polymer derived from a fluorochemical urethane (meth)acrylate monomer for imparting stain release properties to a substrate
DE19724948A1 (de) * 1997-06-12 1998-12-17 Wacker Chemie Gmbh (Meth)acrylatgruppen und Oxyalkylengruppen aufweisende Organosiliciumverbindungen
AU1383699A (en) * 1997-11-06 1999-05-31 Edgington Company, The Coating composition
US6589650B1 (en) * 2000-08-07 2003-07-08 3M Innovative Properties Company Microscope cover slip materials
US6224949B1 (en) * 1998-06-11 2001-05-01 3M Innovative Properties Company Free radical polymerization method
US6238798B1 (en) * 1999-02-22 2001-05-29 3M Innovative Properties Company Ceramer composition and composite comprising free radically curable fluorochemical component
JP3760669B2 (ja) 1999-04-22 2006-03-29 株式会社Ｎｈｖコーポレーション ハードコートシートとその製造方法
US6299799B1 (en) * 1999-05-27 2001-10-09 3M Innovative Properties Company Ceramer compositions and antistatic abrasion resistant ceramers made therefrom
IT1312344B1 (it) * 1999-06-03 2002-04-15 Ausimont Spa Composizioni per film a basso indice di rifrazione.
EP1246856B1 (en) * 1999-10-27 2009-07-15 3M Innovative Properties Company Fluorochemical sulfonamide surfactants
US6403760B1 (en) * 1999-12-28 2002-06-11 Omnova Solutions Inc. Monohydric polyfluorooxetane polymer and radiation curable coatings containing a monofunctional polyfluorooxetane polymer
JP2001301053A (ja) 2000-04-20 2001-10-30 Sony Corp 非球面複合層を持った接合レンズの成形方法
JP2002006102A (ja) 2000-06-19 2002-01-09 Nof Corp 近赤外線遮蔽性減反射材およびその用途
US6452038B1 (en) * 2000-06-28 2002-09-17 3M Innovative Properties Company Fluoroalkyloxy dispersant
US6558803B1 (en) 2000-07-03 2003-05-06 Adhesives Research Inc. Ambifunctional perfluorinated polyethers
AU8114101A (en) 2000-08-07 2002-02-18 3M Innovative Properties Co Information display protectors
US20020115820A1 (en) * 2001-01-25 2002-08-22 Fang Wang Hyperbranched fluorinated multifunctional alcohols and derivatives
US6803109B2 (en) * 2001-03-09 2004-10-12 3M Innovative Properties Company Water-and oil-repellency imparting urethane oligomers comprising perfluoroalkyl moieties
JP4285238B2 (ja) 2001-09-11 2009-06-24 ダイキン工業株式会社 含フッ素不飽和化合物、含フッ素重合体、およびそれらを用いた硬化性組成物
WO2003022935A1 (en) * 2001-09-11 2003-03-20 3M Innovative Properties Company Smudge resistant nanocomposite hardcoats and methods for making same
US6841079B2 (en) * 2002-05-31 2005-01-11 3M Innovative Properties Company Fluorochemical treatment for silicon articles
AU2003244153A1 (en) 2002-06-27 2004-01-19 Tdk Corporation Object with composite hard coating layer and method of forming composite hard coating layer
US7342080B2 (en) 2004-05-07 2008-03-11 3M Innovative Properties Company Polymerizable compositions, methods of making the same, and composite articles therefrom

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3250808A (en) * 1963-10-31 1966-05-10 Du Pont Fluorocarbon ethers derived from hexafluoropropylene epoxide
US5718833A (en) * 1996-01-16 1998-02-17 Nok Corporation Fluorine-based magnetic fluid

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7342080B2 (en) * 2004-05-07 2008-03-11 3M Innovative Properties Company Polymerizable compositions, methods of making the same, and composite articles therefrom
EP3635022A4 (en) * 2017-05-19 2021-02-24 Etna-Tec, Ltd Process for the preparation of functionalized fluorinated monomers, fluorinated monomers and compositions for the preparation thereof
US11492318B2 (en) 2017-05-19 2022-11-08 Etna-Tec, Ltd. Methods for making functionalized fluorinated monomers, fluorinated monomers, and compositions for making the same

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US20050250928A1 (en) 2005-11-10
JP5065011B2 (ja) 2012-10-31
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ATE485330T1 (de) 2010-11-15
US7288619B2 (en) 2007-10-30

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