[go: up one dir, main page]

WO2008000682A1 - Composés télomériques fluorés et polymères contenant ceux-ci - Google Patents

Composés télomériques fluorés et polymères contenant ceux-ci Download PDF

Info

Publication number
WO2008000682A1
WO2008000682A1 PCT/EP2007/056179 EP2007056179W WO2008000682A1 WO 2008000682 A1 WO2008000682 A1 WO 2008000682A1 EP 2007056179 W EP2007056179 W EP 2007056179W WO 2008000682 A1 WO2008000682 A1 WO 2008000682A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
compounds
carbon atoms
formula
compounds according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2007/056179
Other languages
English (en)
Inventor
Hans Götz
Wolfgang Knaup
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant International Ltd
Original Assignee
Clariant International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Publication of WO2008000682A1 publication Critical patent/WO2008000682A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/80—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • Fluorochemicals are often used as surfactants or wetting agents and are widely used for the surface treatment of substrates. They find frequent utility for the oil-, water-, and soil-repellent finishing of fibrous substrates such as for example carpets, textiles, leather, nonwovens and paper and of hard substrates such as for example wood, metal or concrete. The imbibition of hydrophilic and hydrophobic liquids is reduced with substrates thus treated, and the removal of existing soils is promoted.
  • Perfluoroalkyl iodides obtained via telomerization of telogens with fluorinated monomers such as tetrafiuoroethene, for example, are an important starting point for the preparation of fluorocompounds.
  • Rp is a perfluoroalkyl radical of 1 to 20 carbon atoms
  • A is a group of the formulae
  • R 1 is CF 3 OR 4 , Cl, Br or I,
  • R 2 and R 3 are H, alkyl or aryl
  • R 4 is perfiuoromethyl, perfiuoropropyl or perfiuoropropyloxypropyl
  • perfluoroalkyl iodides are typically first converted with ethene into a perfluoroalkylethyl iodide.
  • the perfluoroalkylethyl iodide can then be converted with suitable reagents into the corresponding perfluoroalkylethyl alcohol.
  • the corresponding (meth)acrylate monomers of the formula I can be prepared.
  • Copolymers prepared from these fluorous acrylates are particularly useful for modifying surfaces to be oil, water and soil repellent, for example for finishing textiles or for coating leather and paper.
  • the raw materials for these compounds are usually obtained from the corresponding non-fluorinated alkylsulphonyl halides by electrochemical fluorination.
  • the corresponding raw materials can also be prepared by reaction of perfluoroalkyl iodides with sulphur dioxide/metal and subsequently with chlorine.
  • Fluorous compounds having a linear perfluoroalkyl chain with 8 fluorinated carbon atoms can degrade to form perfluorooctanecarboxylic acid and perfluorooctanesulphonic acid, respectively. These degradation products are considered not further degradable and therefore are persistent. Moreover, these compounds are suspected of accumulating in living organisms.
  • WO 02/16306 describes branched fluorous (meth)acrylates having the formula III
  • R F (R F ')CHOCOCR CH 2 (III) having a straight-chain or branched perfluoroalkyl group R F of 5 or fewer carbon atoms and a branched perfluoroalkyl chain Rp' of 3 to 5 carbon atoms.
  • R H, CH 3 .
  • WO 02/34848 describes the use of polyoxetanes having trifluoromethyl groups or pentafiuoroethyl groups as perfluoroalkyl radical. This class of compounds likewise represents environmentally compatible perfluoroalkyl-containing compounds used as fluorosurfactants or for coatings.
  • WO 2004/060 964 describes fiuorinated polyethers having a molecular weight of greater than 750 g/mol, which are eliminated particularly easily from the body of living organisms.
  • WO 03/100 158 describes the use of such alcohols and acrylates for finishing textiles.
  • the heretofore described proposals for environmentally friendly alternatives to perfiuoroalkyl compounds are less effective than them when used as a basis for oil- and water-repellent finishes. This is reflected in the values achieved for water repellency and oil repellency and in coating durability.
  • polyfluoroalkyl compounds as hereinbelow defined lead to oil- and water-repellent coatings of high efficiency and durability and are also environmentally compatible.
  • the present invention provides fiuorous telomeric compounds of the formula IV:
  • R 1 is CF 3 OR 4 , Cl, Br or I,
  • R 2 is H or alkyl of 1 to 6 carbon atoms
  • R 3 is alkylene of 1 to 13 carbon atoms
  • R 4 is perfluoromethyl, perfluoropropyl or perfluoropropyloxypropyl
  • X and Y are H, Cl or F
  • OCOCCH 3 CH 2 M is an alkali metal, ammonium mono-, di-, tri- or tetra-Ci-C 4 -alkylammonium cation, a is from 0 to 10 and b is from 1 to 30.
  • fluorous compounds of the formula IV which have a molecular weight of greater than 750 g/mol.
  • Particular preference is given to compounds of the formula IV which have a molecular weight of greater than 1000 g/mol.
  • the polyfluoroalkyl radical Rp can be a polyfiuoroalkyl group having a unitary chain length or a mixture of polyfluoroalkyl groups having different chain lengths, for example CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 6 F n , C 8 F n , Ci 0 F 2 I, Ci 2 F 25 , Ci 4 F 29 and Ci 6 F 3 I groups.
  • the polyfluoroalkyl radical can be branched or unbranched.
  • R 1 is a sterically voluminous group which has a crystallization-inhibiting effect on the polyfluoroalkyl chain. Particular preference is given either to a perfluoromethyl group, to a perfluoroalkyl ether group or to a chlorine, bromine or iodine atom. A perfluoromethyl group is most preferable.
  • R 2 may be hydrogen or an aryl chain of 1 to 6 carbon atoms.
  • R 2 is a methyl or ethyl group.
  • R 3 is an alkylene group of 1 to 13 carbon atoms.
  • R 3 is preferably an ethylene group.
  • One aspect of the invention concerns the production of copolymers of the methacrylate- or acrylate-functionalized telomeric compounds of the formula (IV).
  • the present invention further provides for the use of the specified compounds, or of their copolymers, for applications where the surface energy of a substrate is lowered.
  • the present invention further provides for the use of the hereindescribed copolymers in the manufacture of compositions used in conferring oil, water and soil repellency on fibrous substrates such as, for example, carpets, textiles, leather, nonwovens and paper and on hard substrates such as, for example, wood, metal or concrete.
  • R 4 is a perfiuoromethyl group, a perfiuoropropyl group or a perfiuoropropyloxypropyl group.
  • a perfiuoromethyl group is most preferable.
  • R 5"8 is any linear or branched alkyl chain of 1 to 20 carbon atoms.
  • a is from 0 to 10 and more preferably from 0 to 5.
  • b is from 1 to 30 and more preferably a + b > 3.
  • X and Y may independently be H, Cl or F.
  • X and Y are fluorine atoms.
  • X is a fluorine atom and Y is a chlorine atom, or X and Y are hydrogen atoms.
  • telomerization a fluorous compound (telogen) capable of transferring a free radical chain is reacted with at least one fluorinated monomer (taxogen) via a free radical forming mechanism at 20-250 0 C to form the telomer of the formula
  • Useful telogens include fluorous alkyl compounds having a group to be scissioned free- radically, for example fluorous alkyl iodides, bromides, thiols, thioethers and alcohols. Preference is given to perfluoroalkyl iodides having a unitary chain length or to a mixture of perfluoroalkyl iodides having different chain lengths.
  • the perfluoroalkyl radical can be branched or unbranched, for example perfiuoromethyl iodide, perfluoroethyl iodide, n-perfluoropropyl iodide, isoperfluoropropyl iodide, n- perfluorobutyl iodide, isoperfluorobutyl iodide, tert-perfluorobutyl iodide and isomers of perfluorohexyl iodide, perfluorooctyl iodide, perfluorodecyl iodide and perfluorododecyl iodide and so on.
  • perfluoroalkyl iodides in accordance with the invention having a chain length of 1 to 20 carbon atoms and at least one terminal CF 3 group.
  • perfiuoromethyl iodide perfiuoroethyl iodide, perfiuoropropyl iodide or perfluoroisopropyl iodide or a technical grade mixture of various perfluoroalkyl iodides, having chain lengths of 6 to 16 fiuorinated carbon atoms or 8 to 16 fiuorinated carbon atoms and an average chain length of about 7.5 fiuorinated carbon atoms or about 9 fiuorinated carbon atoms.
  • the addition of the taxogens onto the telogen results in the building up of higher molecular weights.
  • the telomer thus formed consists of a perfluoroalkyl chain having a terminal iodine group.
  • the way the taxogens are incorporated in the telomer differs according to which of the following three variants is chosen.
  • R 1 likewise exhibits blockwise incorporation of the monomers, but with the added monomers in the reverse order.
  • Examples of compounds of the formula are: chlorotrifiuoroethene, bromotrifluoroethene, iodotrifiuoroethene, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluoropropyloxypropyl vinyl ether and also branched and unbranched perfiuoroolefins having a terminal double bond, examples being hexafiuoropropene, 1-perfiuorobutene, 1-perfiuorohexene or perfluorooctene.
  • free radicals which initiate the telomerization reactions can be generated by sources capable of forming free radicals.
  • Useful sources for forming free radicals include light or heat.
  • the light source typically has its maximum in the infrared to ultraviolet region. Free radical formation due to heat typically takes place at temperatures between 100 0 C and 250 0 C.
  • Useful sources for forming free radicals further include free radical initiators of the chemical kind, which are also capable of lowering the reaction temperature required for free radical formation to between 0 0 C and 150 0 C, examples being organic or inorganic peroxides, azo compounds, organic and inorganic metal compounds and metals and also combinations thereof. Particular preference is given to persulphates, fiuorinated and nonfiuorinated organic peroxides, azo compounds and metals such as for example Ru, Cu, Ni, Pd and Pt.
  • the telomerization can be carried solventlessly, in solution, in suspension or emulsion.
  • the reaction without a solvent or in emulsion is particularly preferred.
  • the telogen is first converted with the aid of surfactants into an aqueous emulsion.
  • the emulsion can be stabilized by anionic, cationic, nonionic or amphoteric surfactants and combinations thereof. Fluorosurfactants are particularly suitable for example.
  • the reaction typically takes place at elevated temperature through addition of the taxogens and free radical initiators. Additional components can increase the reaction yield, examples being small amounts of aqueous solutions of sulphites, bisulphites or dithionates.
  • the polyfluoroalkyl iodides can be reacted in a reaction as described in DE 2 915 800 in the presence of suspensions of pulverulent metals such as for example iron, cobalt and nickel and also their mixtures in organic solvents, with SO 2 and then with Cl 2 .
  • pulverulent metals such as for example iron, cobalt and nickel and also their mixtures in organic solvents
  • Useful organic solvents include N,N-dimethylformamide, N,N- dimethylacetamide and N-methylpyrrolidone in pure form or as mixtures with polar solvents, for example nitriles such as acetonitrile, open-chain ethers such as diethyl ether, dimethylglycol or dimethyldiglycol, cyclic ethers such as tetrahydrofuran or 1,4- dioxane, ketones such as acetone or hexamethylphosphoramide.
  • polar solvents for example nitriles such as acetonitrile, open-chain ethers such as diethyl ether, dimethylglycol or dimethyldiglycol, cyclic ethers such as tetrahydrofuran or 1,4- dioxane, ketones such as acetone or hexamethylphosphoramide.
  • polar solvents for example nitriles such as acetonitrile, open-chain ethers such
  • the bulk of the solvent is distilled off and water is added only for elemental chlorine to be subsequently used at a temperature of 0 0 C to 100 0 C, which brings about the conversion to the polyfluoroalkylsulphonyl chloride.
  • the polyfluoroalkylsulphonic acid can also be obtained by primary hydrolysis of the polyfluoroalkylsulphonyl chloride with a base and subsequent acidification.
  • a base such as, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, caesium hydroxide or ammonium hydroxide.
  • This reaction can be carried out at temperatures between 40 0 C and 80 0 C with or without solvent.
  • Useful primary amino alcohols include for example 2- aminoethanol, 3-aminopropanol, 4-aminobutanol, 2-amino-l-butanol, 5-aminopentanol, 2-amino-l-pentanol, 6-aminohexanol and useful secondary amino alcohols include for example 2-methylaminoethanol, 3-methylaminopropanol, 4-methylaminobutanol, 2- methylamino-1-butanol, 5-methylaminopentanol, 2-methylamino-l-pentanol, 6- methylaminohexanol, 2-ethylaminoethanol, 3-ethylaminopropanol, A- ethylaminobutanol, 2-ethylamino-l-butanol, 5-ethylaminopentanol, 2-ethylamino-l- pentanol, 6-ethylaminohexanol, 2-propyla
  • a primary amine such as for example n-ethylamine, n-propylamine, isopropylamine or n-butylamine is reacted under the same conditions as described above.
  • the polyfluoroalkylsulphonamide thus formed is converted with the aid of a strong base such as for example sodium methoxide into the corresponding amide salt.
  • the salt is reacted with a halogen- containing alcohol to form the polyfluoroalkyl sulphonamido alcohol.
  • a halogen-containing alcohol to form the polyfluoroalkyl sulphonamido alcohol.
  • This reaction can be carried out at temperatures between 80 0 C and 150 0 C with or without solvent.
  • the product is neutralized and purified by washing, extraction or distillation.
  • the halogen-containing alcohol are 2-chloroethanol, 3-chloropropanol, 2- chloropropanol, and 4-chlorobutanol.
  • the reaction with the (meth)acrylate acid chlorides is typically carried out in the presence of a base such as triethylamine to bind hydrogen chloride formed.
  • a suitable catalyst for example a tin catalyst, can be used for the transesterification.
  • the optional comonomer (b) is not fiuorous (does not contain fluorine) and can represent a multiplicity of commercially available acrylates and methacrylates and styrene derivatives.
  • nonfluorinated comonomers are hydrocarbyl esters and amides of unsaturated carboxylic acids. These include for example the following esters and amides of acrylic acid, methacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid: vinyl, allyl, methyl, ethyl, propyl, isopropyl, n- butyl, isobutyl, t-butyl, hexyl, 3,3-dimethylbutyl, heptyl, octyl, isooctyl, lauryl, cetyl, stearyl, behenyl, cyclohexyl, bornyl, isobornyl, phenyl, benzyl, adamantyl, tolyl, (2,2- dimethyl-l-methyl)propyl, cyclopentyl, 2-ethylhexyl,
  • allyl esters and vinyl esters such as for example allyl acetate, vinyl acetate, allyl heptanoate and vinyl heptanoate; alkyl vinyl ethers and alkyl allyl ethers such as for example cetyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether and ethyl vinyl ether; ⁇ , ⁇ -unsaturated nitriles such as for example acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -cyanoethyl acrylate; aminoalkyl (meth)acrylates such as for example N,N-diethylaminoethyl (meth)acrylate, N-t-butylaminoethyl (meth)acrylate; alkyl (meth)acrylates having an ammonium group such as for example 2-methacryloyloxyethyl
  • Particularly preferred optional comonomers (b) can be the following esters or amides of acrylic acid and methacrylic acid: methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl, myristyl, lauryl, octadecyl, methoxy poly(ethylene glycol) and methoxy poly(propylene glycol) as described above.
  • the comonomer (c) contains one or more crosslinkable groups.
  • a crosslinkable group is a functional group capable of entering a reaction with the substrate and/or with a further polyfunctional compound added.
  • Such crosslinkable groups can be: carboxylic acid groups, ethylenically unsaturated groups, hydroxyl groups, amino groups, N- alkylolamide groups, isocyanate groups or protected isocyanate groups.
  • Examples of comonomers having one or more crosslinkable groups include unsaturated carboxylic acids and anhydrides of acrylic acid, methacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, monomers including a hydroxyl group, for example hydroxyethyl (meth)acrylates and hydroxypropyl (meth)acrylates, hydroxybutyl (meth)acrylate, poly(ethylene glycol) mono(meth)acrylate, poly(propylene glycol) mono(meth)acrylate, poly(ethylene glycol)-co-poly(propylene glycol) mono(meth)acrylate, polytetrahydrofuran mono(meth)acrylate, N- hydroxymethyl(meth)acrylamide, hydroxybutyl vinyl ether.
  • crosslinkable monomers are for example vinyl (meth)acrylate, allyl (meth)acrylate, N- methoxymethylacrylamide, N-isopropoxymethylacrylamide, N- butoxymethylacrylamide, N-isobutoxymethylacrylamide, glycidyl (meth)acrylate and ⁇ , ⁇ -dimethyl-m-isopropenylbenzyl isocyanate.
  • Other examples are monomers which release isocyanates at elevated temperatures or under irradiation with light, examples being phenol-, ketoxime- and pyrazole-protected isocyanate-terminated alkyl (meth)acrylates.
  • the optional comonomer (d) is chlorine containing.
  • chlorine-containing comonomers are halogenated olefinic hydrocarbons such as for example vinyl chloride, vinylidene chloride, 3-chloro-l-isobutene, 1-chlorobutadiene, 1,1-dichlorobutadiene and 2,5-dimethyl-l,5-hexadiene.
  • Vinylidene chloride and vinyl chloride are particularly preferred optional comonomers (c).
  • the copolymer described hereby is typically prepared by a free radical polymerization technique, for example by solvent, emulsion, microemulsion or miniemulsion polymerization techniques. Variants of the emulsion polymerization are particularly preferred.
  • the emulsion polymerization of the monomers takes place in the presence of water, surfactants and an optional organic solvent.
  • the mixture can have been pre- emulsified before the polymerization, by means of a high pressure homogenizer or a similar apparatus.
  • the polymerization is typically carried out at temperatures between 50 0 C and 150 0 C in the presence of a free radical initiator.
  • nonionic surfactants include poly(ethylene glycol) lauryl ether, poly(ethylene glycol) tridecyl ether, poly(ethylene glycol) cetyl ether, poly(ethylene glycol)-co-poly(propylene glycol) cetyl ether, poly(ethylene glycol) stearyl ether, poly(ethylene glycol) oleyl ether, poly(ethylene glycol) nonylphenol ether, poly(ethylene glycol) octylphenol ether, poly(ethylene glycol) monolaurate, poly(ethylene glycol) monostearate, poly(ethylene glycol) monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, poly(ethylene glycol) lauryl ether, poly(ethylene glycol) tridecyl ether, poly(ethylene glycol) cety
  • Examples of the cationic surfactants in accordance with the invention are ammonium compounds based on saturated and unsaturated fatty acid amines, for example octadecylammonium acetate, dodecyltrimethylammonium chloride; ammonium compounds based on amino-functionalized polyethoxylates and polypropoxylates and their interpolymers such as for example polyoxyethylene laurylmonomethylammonium chloride; ammonium compounds based on arylamines such as for example biphenyltrimethylammonium chloride, imidazoline derivatives such as for example ammonium salts formed from tallow and imidazoline; silicone-based cationic surfactants and fluorine-based cationic surfactants.
  • ammonium compounds based on saturated and unsaturated fatty acid amines for example octadecylammonium acetate, dodecyltrimethylammonium chloride
  • the amount of cationic surfactant used ranges from 0.1 to 100 percent by weight relative to the weight of the polymer.
  • the anionic surfactants in accordance with the invention include fatty alcohol sulphates, for example sodium dodecylsulphate and poly(ethylene glycol) lauryl ether sulphate; alkylsulphonates such as for example sodium laurylsulphonate; alkylbenzenesulphonates, for example nonylphenol ether sulphates, sulphosuccinates, for example sodium hexyl diether sulphosuccinate; fatty alcohol phosphates, for example sodium laurylphosphate and fatty acid salts, such as for example sodium stearic acid salt.
  • the amount of anionic surfactant used ranges from 0.1 to 100 percent by weight, relative to the weight of the polymer.
  • free radical initiators are organic or inorganic peroxides, azo compounds, organic and inorganic metal compounds and metals and also combinations thereof. Particular preference is given to azo compounds such as azobisisobutyronitriles (AIBNs), azobisvaleronitrile and azobis(2-cyanovaleric acid), 2,2'-azobis(2- amidinopropane) dihydrochloride; hydroperoxides such as cumene hydroperoxide, t- butyl hydroperoxide and t-amyl hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide, peroxyesters such as t-butyl perbenzoate and di-t-butyl peroxyphthalate, diacyl peroxides, such as benzoyl peroxide and lauroyl peroxide; inorganic peroxides such as ammonium persulphate and potassium persulphate and also combinations of the specified compounds with organic or inorgan
  • a chain transfer agent can be used in the polymerization, an example being an alkylthiol.
  • Examples of the organic solvent in the solvent and emulsion polymerization are: ketones such as for example acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohols such as for example ethanol, isopropanol and butanol, polyalcohols such as for example 1,3-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and glycerol; ethers and esters of polyalcohols, such as for example dipropylene glycol mono methyl ether, tripropylene glycol mo no methyl ether, triethylene glycol dimethyl ether and diethylene glycol monobutyl ether acetate; esters such as for example ethyl acetate, propyl acetate, butyl acetate, dibutyl adipate and dibutyl succinate; hydrocarbons and halogenated hydrocarbon
  • the preferred solids content for the polymer dispersion prepared is between 20 and 40 percent by weight.
  • the fiuorous copolymers containing a fiuorous monomer of the formula IV are suitable for coating fibrous substrates such as for example carpets, textiles, leather, nonwovens or paper or hard substrates such as for example wood, metal or concrete. They endow these substrates with water-, oil- and soil-repellent properties.
  • the invention thus also provides a process for surface treatment of fibrous substrates with an effective amount of the fiuorous aqueous dispersion.
  • the content of the preparation for finishing textiles and other sheetlike structures in accordance with this invention is chosen so that sufficient repellent properties are transferred to the treated substrate.
  • the wet pick-up was determined by weighing the finished specimens before and after application.
  • the fiuorous textile- finishing agents according to the invention can be used together with other additives, including water-repellent materials, such as for example waxes, silicones, zirconium compounds or stearic acid salts, and also other oil-repellent materials, surfactants, insecticides, flame retardants, antistatic additives, plasticizers, dye fixatives and crease resist additives in an amount which does not impair fixing on the textile and the stability of the composition.
  • water-repellent materials such as for example waxes, silicones, zirconium compounds or stearic acid salts
  • oil-repellent materials such as for example waxes, silicones, zirconium compounds or stearic acid salts
  • surfactants such as for example waxes, silicones, zirconium compounds or stearic acid salts
  • surfactants such as for example waxes, silicones, zirconium compounds or stearic acid salts
  • surfactants such as for example waxes, silicones, zi
  • the fiuorous textile- finishing agents according to the invention can be crosslinked by addition of reactive additives such as for example melamine resins, protected isocyanates or epoxides.
  • the fibrous substrates to be coated with the fiuorous polymeric dispersion can be for example carpets, textiles, leather, nonwovens and paper. These consist inter alia of natural fibres such as for example cotton, linen and silk; of synthesis fibres such as for example polyamides, polyesters, polyurethanes, polyolefins, poly(meth)acrylates, poly(vinyl chlorides), poly( vinyl alcohols); semisynthetic fibres such as for example rayon or acetate; inorganic fibres such as for example glass fibres or ceramic fibres or any desired combination of the specified fibres or any desired combination of woven products composed of these materials.
  • natural fibres such as for example cotton, linen and silk
  • synthesis fibres such as for example polyamides, polyesters, polyurethanes, polyolefins, poly(meth)acrylates, poly(vinyl chlorides), poly( vinyl alcohols)
  • semisynthetic fibres such as for example rayon or acetate
  • inorganic fibres such
  • the substrate is typically immersed in a dilute dispersion consisting of copolymer and optional additives.
  • the dilute dispersion can be sprayed onto the substrate.
  • the saturated substrate is subsequently pressed by a system of rolls to remove excess dispersion, dried in an oven and crosslinked at a temperature and for a time sufficient to ensure crosslinking on the treated substrate.
  • This crosslinking process is typically carried out at temperatures between 50 and about 190 0 C. In general, a temperature of about 120 0 C to 180 0 C and in particular of about 130 0 C to 170 0 C for a period of 20 seconds up to 10 minutes is suitable, preference being given to 5 seconds to 5 minutes.
  • a further alternative for applying the preparation to a substrate is foam application wherein the preparation is applied to the substrate as a foam which is then dried and crosslinked.
  • the preparation is typically added in a concentrated form which has been admixed with an additional foamer.
  • a highly concentrated preparation for foam application typically contains the fluoropolymer in an amount of up to 20% by weight.
  • Water repellency is determined by the spray test as per AATCC Standard Test Method 22. Distilled water is sprayed onto the textile substrate to be tested and a subsequent visual comparison of the pattern of wetting with reference pictures of an evaluation standard recited in the test method was used to generate a numerical value. The reported numerical values relate to the appearance of the surface after spraying with water and have the following connotation (Table 1):
  • a second test with a series of water- isopropanol test solutions can be used to determine the isopropanol repellency (IPA) of a substrate.
  • the reported IPA rating is the highest numbered test solution where the fabric is not wetted within 10 seconds and the drops still have the shape of a sphere or a hemisphere.
  • Wetted substrates or substrates which are only repellent to 100% water (0% isopropanol), i.e. the least wetting test solution, are rated 0, whereas substrates which are repellent to 100% isopropanol (0% water) are rated 10.
  • Intermediate ratings can be assigned as well.
  • Oil repellency as per AATCC Standard Test Method 118 tests the ability of a substrate to repel oily soiling, higher ratings in the assessment scale denoting better repellency of such soil, in particular of oily liquids.
  • drops of standardized test liquids consisting of a selected series of hydrocarbons having different surface tensions, are applied in succession to the surface of the specimen to be tested, by careful pipetting, and the wetting is visually assessed after a defined contact time.
  • the oil repellency value corresponds to the highest numbered test liquid which causes no wetting of the surface.
  • the standard test liquids have the following composition (Table 2): Table 2
  • Nujol is a mineral oil from Plough Inc. having a Saybolt viscosity of 360/390 at 38°C and a specific weight of 0.880/0.900 at 15°C.
  • the pressure is kept constant at 17 bar until 82.5 g (0.55 mol) of hexafiuoropropene and 90 g (0.90 mol) of tetrafluoroethene have been added. After a drop in pressure, the autoclave is cooled down to room temperature and the fluorochemical phase is separated off by addition of salt and washed. The low molecular weight constituents are separated off by distillation. The iodine content of 11.2% suggests an average molecular weight of about 1400 g/mol.
  • the compound designated 1812 is a perfiuoroalkyl iodide mixture having 6 to 14 fluorinated carbon atoms per molecule having an average chain length of about 9 fluorinated carbon atoms.
  • Fluorolink C is a perfiuoro polyether carboxylic acid.
  • Example 1 was repeated to prepare corresponding polyfluoroalkyl iodides (Examples 2 to 10). The results of the syntheses are shown in Table 3.
  • Fluowet 1612 and Fluowet 1812 are perfiuoroalkyl iodide mixtures from Clariant, each having 6 to 14 fiuorinated carbon atoms per molecule having an average chain length of about 7.5 fiuorinated carbon atoms and 9 fiuorinated carbon atoms respectively.
  • Examples 12 to 20 Synthesis of polyfluoroalkylsulphonyl chlorides Example 11 was repeated to prepare corresponding polyfluoroalkylsulphonyl chlorides (Examples 12 to 20). The results of the syntheses are reported in Table 4.
  • Example 21 Synthesis of C 8 Fi 7 (CF 2 CF(CF 3 ) a (CF 2 CF 2 ) b SO 2 N(CH 3 )CH 2 CH 2 OH
  • a nitrogen-purged 1 litre three neck flask equipped with stirrer, thermometer and a reflux condenser was charged with 300 ml of methyl tert-butyl ether and 92.2 g of N- methylethanol (1.23 mol) with stirring.
  • 576.9 g of the polyfluoroalkylsulphonyl chloride from Example 11 (0.41 mol) were introduced over 4 hours, which was followed by a further 3 hours of stirring at 30 0 C.
  • reaction mixture was washed with 200 ml of dilute hydrochloric acid (10% strength) and repeatedly with water.
  • the solvent was distilled off to leave 533.6 g of polyfluoroalkyl sulphonamido alcohol having a hydroxyl content of 1.22% of OH.
  • Examples 22 to 30 Synthesis of polyfluoroalkyl sulphonamido alcohols Example 21 was repeated to prepare corresponding polyfluoroalkyl sulphonamido alcohols (Examples 22 to 30). The results of the syntheses are reported in Table 4.
  • a three neck flask was charged with 91.0 g (0.06 mol) of the alcohol from Example 21, 23.0 g of acrylic acid, 0.3 g of methanesulphonic acid and 0.4 g of p-methoxyphenol and this initial charge was heated to 8O 0 C.
  • the water of reaction was separated during the reaction within 24 hours at the reaction temperature and a pressure of 200 mbar.
  • the organic phase was repeatedly washed with warm water and dried in a rotary evaporator.
  • Example 31 was repeated to convert the polyfluoroalkyl amido alcohols into polyfluoroalkyl acrylates (AC) or, with methacrylic acid, into polyfluoroalkyl (meth)acrylates (MA).
  • the compositions are reported in Table 5.
  • Table 5 Table 5
  • Example 41 Preparation of a dispersion for textile finishing (recipe 1) The dispersion was prepared by intensively stirring the following components in a four neck flask equipped with stirrer, reflux condenser, inert gas supply and internal thermometer:
  • the emulsion was heated to 60 0 C under a constant stream of nitrogen. Then, 0.2 g of the initiator 2,2'-azo-bis-isobutyronitrile (AIBN) was added. The polymerization time was 10 hours at 60 0 C.
  • AIBN 2,2'-azo-bis-isobutyronitrile
  • the resulting dispersion had a solids content of about 34%.
  • the dispersion was acidified and diluted to 30 g/1.
  • the dispersion was applied to fibrous substrates on an HVF 59301 laboratory pad-mangle from Mathis AG (Switzerland) followed by drying and heat treatment at 160°C/30 seconds in an LTE laboratory dryer from Mathis AG (Switzerland).
  • the commercially available textile Sahara 530306 from NEL GmbH, Neugersdorf, was used as PES/Co 65/35 substrate to compare the applications.
  • the wet pick-up was about 66% for all examples recited.
  • the washing/drying procedure included 5 wash cycles at 60 0 C.
  • the corresponding pieces of fabric were made up with ballast fabric to a wash load of one kilogram.
  • the amount of laundry detergent needed was 7 g of "Coral intensive" per wash cycle.
  • the fabric pieces were not dried between the wash cycles. After washing, the laundry was dried in a laundry dryer.
  • Example 42 Preparation of a dispersion for textile finishing (recipe 2) To prepare the dispersion, the following components were intensively stirred under an inert gas atmosphere in an autoclave equipped with a stirrer, reflux condenser and internal thermometer:
  • polyfluoroalkyl acrylate from Example 31
  • LA lauryl acrylate
  • VC vinyl chloride
  • N-MAM N-methoxymethylacrylamide
  • nonionic surfactant B 4.0 g of lauryltrimethylammonium chloride (cationic surfactant B) 200.0 g of water
  • the resulting dispersion had a solids content of about 38%.
  • the dispersion was acidified and diluted to 30 g/1.
  • Application to textile substrates was carried as described in Example 41.
  • Example 43 Preparation of a dispersion for textile finishing (recipe 3) To prepare the dispersion, the following components were intensively stirred under an inert gas atmosphere in an autoclave equipped with a stirrer, reflux condenser and internal thermometer:
  • the resulting dispersion had a solids content of about 36%.
  • the dispersion was acidified and admixed with Cassurit HML (Clariant) and 20% by weight aqueous magnesium chloride solution, so that the concentration per 1 of liquor was in each case 30 g.
  • Application to textile substrates was carried out as described in Example 41.
  • Examples 44-47 Preparation, application and testing of dispersions for textile finishing similarly to Example 41
  • Examples 48-51 Preparation, application and testing of dispersions for textile finishing similarly to Example 42
  • Examples 57-60 Synthesis of polyfluoroalkylsulphonic acid salts Example 56 was repeated to convert the polyfluoroalkylsulphonyl chloride of Example 11 into the corresponding polyfluoroalkylsulphonic acid salts by reaction with sodium hydroxide, lithium hydroxide and ammonium hydroxide.
  • Examples 62-70 Synthesis of polyfluoroalkylsulphonic acids Example 61 was repeated to hydro lyse the polyfluoroalkylsulphonyl chlorides of Examples 12 to 20 to the polyfluoroalkylsulphonic acids.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne des composés télomériques fluorés de formule RF - A -SO2 - Z, dans laquelle RF représente un radical perfluoroalkyle comprenant entre 1 et 20 atomes de carbone; A représente un groupe de formules (I) ou (II) dans lesquelles R1 représente CF3, OR4, Cl, Br ou I; R2 représente H ou alkyle comprenant entre 1 et 6 atomes de carbone; R3 représente alkylène comprenant entre 1 et 13 atomes de carbone; R4 représente perfluorométhyle, perfluoropropyle ou perfluoropropyloxypropyle; X et Y représentent H, Cl ou F; Z représente -OH, -Cl, -OM, -N(R2)R3OH, -N(R2)R3OCOCH = CH2 ou - Z N(R2)R3OCOCCH3 = CH2 ; M représente un métal alcalin, ammonium ou un mono-, di-, tri- ou tétra-C1-C4- cation d'alkylammonium; a est compris entre 0 et 10 et b est compris entre 1 et 30. Ces composés sont copolymérisés avec d'autres monomères. Les copolymères ainsi obtenus sont utiles pour la finition hydrofuge, oléofuge et antitaches de substrats fibreux.
PCT/EP2007/056179 2006-06-27 2007-06-21 Composés télomériques fluorés et polymères contenant ceux-ci Ceased WO2008000682A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006029375.4 2006-06-27
DE102006029375 2006-06-27

Publications (1)

Publication Number Publication Date
WO2008000682A1 true WO2008000682A1 (fr) 2008-01-03

Family

ID=38441458

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/056179 Ceased WO2008000682A1 (fr) 2006-06-27 2007-06-21 Composés télomériques fluorés et polymères contenant ceux-ci

Country Status (2)

Country Link
TW (1) TW200808834A (fr)
WO (1) WO2008000682A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8026289B2 (en) 2008-10-21 2011-09-27 E.I. Du Pont De Nemours And Company Fluorinated polyoxyalkylene glycol diamide surfactants
EP3041813A4 (fr) * 2013-09-04 2017-04-26 Honeywell International Inc. Agents tensioactifs fluorés présentant une biodégradabilité améliorée

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2950317A (en) * 1957-10-21 1960-08-23 Minnesota Mining & Mfg Process for preparation of perfluoroalkyl sulfonyl chlorides
US3636085A (en) * 1969-04-01 1972-01-18 Ciba Geigy Corp Perfluoroalkylsulfonamido - alkyl esters of fumaric acid and other ethylenically unsaturated polybasic acids and polymers thereof
FR2093605A5 (fr) * 1970-05-22 1972-01-28 Bayer Ag
FR2262145A1 (fr) * 1974-02-26 1975-09-19 Minnesota Mining & Mfg
US4098806A (en) * 1976-03-05 1978-07-04 Produits Chimiques Ugine Kuhlmann Process for functionalizing perfluorohalogenoalkanes
DE2754457A1 (de) * 1977-12-07 1979-06-13 Hoechst Ag Verfahren zur herstellung von perfluoralkansulfonsaeuren
US4288646A (en) * 1979-10-05 1981-09-08 Pcuk Produits Chimiques Ugine Kuhlmann Regioselective preparation of β-isopropylnaphthalene over superacidic solid or supported perfluorinated sulfonic acid catalysts
GB2082178A (en) * 1980-08-18 1982-03-03 Ugine Kuhlmann Hydration of Lower Olefins to Alcohols over Solid Superacidic Perfluorinated Sulfonic Acid Catalyst
EP0109171A1 (fr) * 1982-10-13 1984-05-23 Minnesota Mining And Manufacturing Company Copolymères fluorés, papiers enfournables et fibres textiles ainsi traitées
US5118879A (en) * 1989-02-27 1992-06-02 Nippon Oil And Fats Co., Ltd. Fluoroalkyl derivative and process for preparing the same
EP0526976A1 (fr) * 1991-07-10 1993-02-10 Minnesota Mining And Manufacturing Company L'halogénure de perfluoroalkyle et leurs dérivés
WO1993010085A1 (fr) * 1991-11-12 1993-05-27 Minnesota Mining And Manufacturing Company Derives de l'acide dimere fluoroaliphatique et leur utilisation
FR2704099A1 (fr) * 1993-04-15 1994-10-21 Centre Nat Etd Spatiales Electrolyte pour accumulateur électrique.
EP0656440A2 (fr) * 1993-11-29 1995-06-07 Minnesota Mining And Manufacturing Company Agent hydrofuge et oleofuge contenant du fluor
US5518788A (en) * 1994-11-14 1996-05-21 Minnesota Mining And Manufacturing Company Antistatic hard coat incorporating a polymer comprising pendant fluorinated groups
WO1996018691A2 (fr) * 1994-12-12 1996-06-20 Minnesota Mining And Manufacturing Company Composition de revetement possedant des proprietes antireflet et anti-buee
US5827919A (en) * 1995-10-06 1998-10-27 E. I. Du Pont De Nemours And Company Fluorourethane additives for water-dispersed coating compositions
JPH10338790A (ja) * 1996-11-29 1998-12-22 Kureha Chem Ind Co Ltd 半導電性樹脂組成物
EP1088558A2 (fr) * 1999-09-29 2001-04-04 Schering Aktiengesellschaft Formulations galéniques

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2950317A (en) * 1957-10-21 1960-08-23 Minnesota Mining & Mfg Process for preparation of perfluoroalkyl sulfonyl chlorides
US3636085A (en) * 1969-04-01 1972-01-18 Ciba Geigy Corp Perfluoroalkylsulfonamido - alkyl esters of fumaric acid and other ethylenically unsaturated polybasic acids and polymers thereof
FR2093605A5 (fr) * 1970-05-22 1972-01-28 Bayer Ag
FR2262145A1 (fr) * 1974-02-26 1975-09-19 Minnesota Mining & Mfg
US4098806A (en) * 1976-03-05 1978-07-04 Produits Chimiques Ugine Kuhlmann Process for functionalizing perfluorohalogenoalkanes
DE2754457A1 (de) * 1977-12-07 1979-06-13 Hoechst Ag Verfahren zur herstellung von perfluoralkansulfonsaeuren
US4288646A (en) * 1979-10-05 1981-09-08 Pcuk Produits Chimiques Ugine Kuhlmann Regioselective preparation of β-isopropylnaphthalene over superacidic solid or supported perfluorinated sulfonic acid catalysts
GB2082178A (en) * 1980-08-18 1982-03-03 Ugine Kuhlmann Hydration of Lower Olefins to Alcohols over Solid Superacidic Perfluorinated Sulfonic Acid Catalyst
EP0109171A1 (fr) * 1982-10-13 1984-05-23 Minnesota Mining And Manufacturing Company Copolymères fluorés, papiers enfournables et fibres textiles ainsi traitées
US5118879A (en) * 1989-02-27 1992-06-02 Nippon Oil And Fats Co., Ltd. Fluoroalkyl derivative and process for preparing the same
EP0526976A1 (fr) * 1991-07-10 1993-02-10 Minnesota Mining And Manufacturing Company L'halogénure de perfluoroalkyle et leurs dérivés
WO1993010085A1 (fr) * 1991-11-12 1993-05-27 Minnesota Mining And Manufacturing Company Derives de l'acide dimere fluoroaliphatique et leur utilisation
FR2704099A1 (fr) * 1993-04-15 1994-10-21 Centre Nat Etd Spatiales Electrolyte pour accumulateur électrique.
EP0656440A2 (fr) * 1993-11-29 1995-06-07 Minnesota Mining And Manufacturing Company Agent hydrofuge et oleofuge contenant du fluor
US5518788A (en) * 1994-11-14 1996-05-21 Minnesota Mining And Manufacturing Company Antistatic hard coat incorporating a polymer comprising pendant fluorinated groups
WO1996018691A2 (fr) * 1994-12-12 1996-06-20 Minnesota Mining And Manufacturing Company Composition de revetement possedant des proprietes antireflet et anti-buee
US5827919A (en) * 1995-10-06 1998-10-27 E. I. Du Pont De Nemours And Company Fluorourethane additives for water-dispersed coating compositions
JPH10338790A (ja) * 1996-11-29 1998-12-22 Kureha Chem Ind Co Ltd 半導電性樹脂組成物
EP1088558A2 (fr) * 1999-09-29 2001-04-04 Schering Aktiengesellschaft Formulations galéniques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
OKAZOE T ET AL: "An entirely new methodology for synthesizing perfluorinated compounds: synthesis of perfluoroalkanesulfonyl fluorides from non-fluorinated compounds", JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER, AMSTERDAM, NL, vol. 125, no. 11, November 2004 (2004-11-01), pages 1695 - 1701, XP004669204, ISSN: 0022-1139 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8026289B2 (en) 2008-10-21 2011-09-27 E.I. Du Pont De Nemours And Company Fluorinated polyoxyalkylene glycol diamide surfactants
EP3041813A4 (fr) * 2013-09-04 2017-04-26 Honeywell International Inc. Agents tensioactifs fluorés présentant une biodégradabilité améliorée

Also Published As

Publication number Publication date
TW200808834A (en) 2008-02-16

Similar Documents

Publication Publication Date Title
EP2057201B1 (fr) Copolymères de méthacrylate de perfluoroalkyléthyle lyophobes, hydrophobes et résistant aux salissures
KR100752462B1 (ko) 불소 함유 중합체를 포함하여 이루어지는 표면 처리제
JP5493860B2 (ja) 含フッ素重合体およびこれを有効成分とする表面改質剤
JP2012097125A (ja) 含フッ素重合体を有効成分とする表面改質剤
TWI448479B (zh) Antifouling agent composition and its manufacturing method and processing article
CN101573315B (zh) 长链聚亚甲基卤调聚物
CA2675628A1 (fr) Compositions de fluoropolymere et procede d'utilisation
CA2071596A1 (fr) Halogenures de perfluoroalkyle et leurs derives
CA2330051A1 (fr) Compositions de polymeres antisalissures pout tissus
JP2008189826A (ja) 含フッ素重合体からなる汚れ脱離剤
CN101495525A (zh) 包含氟化的酰胺的聚(甲基)丙烯酰胺和聚(甲基)丙烯酸酯
EP1976820B1 (fr) Composés télomères fluorés et polymères les contenant
CA2560392A1 (fr) Agent de traitement de surface, monomere contenant du fluor et polymere contenant du fluor
WO2008000680A1 (fr) Composes telomeriques fluores et polymeres contenant ceux-ci
JP2009242679A (ja) 高純度の含フッ素モノマー組成物およびその重合体からなる表面処理剤
JP6693571B2 (ja) 含フッ素重合体およびこれを有効成分とする防錆剤
CN100526344C (zh) 含氟单体、含氟聚合物以及表面处理剂
WO2008000681A1 (fr) Composés télomères fluorés et polymères les contenant
WO2008000682A1 (fr) Composés télomériques fluorés et polymères contenant ceux-ci
WO2007007743A1 (fr) Fluoropolymere et agent nettoyant
MXPA05002717A (es) Fluoromonomeros, fluoropolimeros, metodos para prepararlos, y su aplicacion a diversas superficies y substratos.
HK1128680A (en) Fluorous telomeric compounds and polymers containing same
WO2007035936A2 (fr) Polymères fluorés contenant du triazole
JP5229005B2 (ja) 含フッ素重合体を含んでなる表面処理剤
HK1134510A (en) Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07786783

Country of ref document: EP

Kind code of ref document: A1

WA Withdrawal of international application
WWW Wipo information: withdrawn in national office

Ref document number: 2007263846

Country of ref document: AU

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU