WO2006028608A1 - Method for treating porous stone using a fluorochemical composition - Google Patents

Method for treating porous stone using a fluorochemical composition Download PDF

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Publication number
WO2006028608A1
WO2006028608A1 PCT/US2005/026810 US2005026810W WO2006028608A1 WO 2006028608 A1 WO2006028608 A1 WO 2006028608A1 US 2005026810 W US2005026810 W US 2005026810W WO 2006028608 A1 WO2006028608 A1 WO 2006028608A1
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Prior art keywords
fluorinated
amount
group
composition
weight
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PCT/US2005/026810
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French (fr)
Inventor
Rudolf J. Dams
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3M Innovative Properties Company
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Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Priority to BRPI0514854-5A priority Critical patent/BRPI0514854A/en
Priority to CA002579163A priority patent/CA2579163A1/en
Priority to AU2005283038A priority patent/AU2005283038A1/en
Priority to CN2005800348803A priority patent/CN101039888B/en
Priority to MX2007002628A priority patent/MX2007002628A/en
Publication of WO2006028608A1 publication Critical patent/WO2006028608A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48Macromolecular compounds
    • C04B41/4838Halogenated polymers
    • C04B41/4842Fluorine-containing polymers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/82Coating or impregnation with organic materials
    • C04B41/83Macromolecular compounds

Definitions

  • the present invention relates to a method of making porous stone water and oil repellent and stain resistant.
  • the invention relates in particular to the use therein of a fluorinated oligomer that is based on repeating units of short chain fluorinated monomers and hydrocarbon monomers.
  • Porous stones are frequently used decoratively in the building industry and outdoor environment. When left unprotected, porous substrates, including porous stone, quickly loose their original appearance from exposure to water- and oil-based stains and gradually deteriorate from water penetration and weathering. Common household liquids are among the most severe stains, including motor oil, cooking oil and beverages, such as coffee and wine. In order to protect porous substrates from oil- and water-based stains, they are often sealed with a film-forming resin, such as an epoxy or urethane product. These coating materials are often quite expensive and may undesirably alter the appearance of the coated substrate. Such coatings also seal the product completely, preventing or greatly reducing the escape of moisture from the coated substrate.
  • a film-forming resin such as an epoxy or urethane product.
  • Fluorochemical-containing treatments have been proposed to render porous substrates resistant to soil and repellent to water- and oil-based stains.
  • US 6,689,854 discloses a water-soluble and shelf-stable aqueous fluorochemical polymeric treatment useful to treat porous substrates to render them repellent to water- and oil-based stains.
  • the treatment comprises a water-soluble or dispersible fluorochemical polymer containing only carbon atoms in the backbone, with a plurality of each of the following groups pendant from the backbone : (a) fluoroaliphatic groups, (b) carboxyl-containing groups, (c) silyl groups and optionally (d) other non-hydrophilic groups.
  • EP 1 225 187 discloses a fluorochemical composition
  • a fluorochemical composition comprising a major amount of an organic solvent and 0.05% by weight to 5% by weight of fluorochemical oligomer dispersed or dissolved in said organic solvent.
  • the compositions are taught to be useful for rendering substrates, in particular ceramics or glass, water and/or oil repellent.
  • US 4,366,300 discloses a compositon for protection of materials against contaminations, spots and stains.
  • the liquid composition comprises by weight 0.1 to 1% of at least one fluorinated resin based on acrylic or methacrylic esters of fluorinated sulfonamido-alcohol, associated or not with non- fluorinated monomers, 0.4 to 10 % of at least one adjuvant selected from aminoplast resins based on melamine, thermoplastic resins and waxes, and 89 to 99.5% of at least one organic solvent.
  • such coating may cause a surface more slippery and prevent water drainage.
  • an alternative treatment for providing porous stone, in particular terracotta, with high water repellency and/or high oil repellency is durable. Further desired properties include good stain resistance and/or stain release. Desirably, the treatment provides good repellency properties when applied at room temperature, dries fast and does not require curing at elevated temperatures. In particular, it would be desirable to find such treatment that can penetrate well into the porous surface of the stone and is highly effective without changing or undesirably diminishing the aesthetical appeal.
  • the present invention relates to a method of treating porous stone, comprising contacting porous stone with a composition comprising:
  • a fluorinated oligomer having a weight average molecular weight of not more than 70,000 g/mol and comprising repeating units derived from one or more hydrocarbon monomers and one or more fluorinated monomers represented by the formula:
  • RrX t -E 1 wherein R f represents a perfluorinated aliphatic group having 3 or 4 carbon atoms, X represents a non-fluorinated organic linking group, t is 0 or 1 and E 1 represents an ethylenically unsaturated group; and wherein the amount of repeating units derived from said fluorinated monomers is more than 50 mole % of the total amount of repeating units;
  • a liquid dispersing or dissolving said fluorinated oligomer comprising an organic solvent in an amount of at least 70% by weight based on the total amount of liquid; and wherein said fluorinated oligomer is contained in said composition in an amount of 1 to 20% by weight based on the total weight of the composition.
  • the method of the present invention may render porous stone water and/or oil repellent.
  • the method may further provide stain repellency to the porous stone as well.
  • the method is generally effective when applied at room temperature, generally shows good penetration. Typically, the treatment shows good durability, even without a heat treatment.
  • the method may be particularly useful for providing terracotta tiles with desired properties including water repellency, oil repellency and stain resistance.
  • the fluorinated oligomers for use in the present invention comprise units derived from at least one hydrocarbon monomer and at least one fluorinated monomer and can be prepared by free-radical polymerization generally in the presence of a chain transfer agent.
  • the fluorinated monomer can typically be represented by the formula : RrX t -E 1 (I) wherein R f represents a perfluorinated aliphatic group having 3 or 4 carbon atoms, X represents a non-fluorinated linking group, t is 0 or 1 and E 1 represents an ethylenically unsaturated group.
  • the perfluorinated aliphatic group R f is a perfluorinated, stable, inert, preferably saturated, non-polar, monovalent aliphatic radical containing 3 or 4 carbon atoms. It can be straight chain or branched chain. Especially suitable fluorinated monomers are those in which the R f -group corresponds to the formula C 4 F 9 -.
  • the linking group X when present, links the perfluoroaliphatic group Rf to the ethylenically unsaturated group E 1 and is generally a non-fluorinated organic linking group.
  • the linking group X may be a hydrocarbon group which may optionally be substituted and which generally contains from 1 to about 20 carbon atoms.
  • X represents a hydrocarbon group, it may optionally contain oxygen, nitrogen, or sulfur- containing groups or a combination thereof, but X should typically be free of functional groups that substantially interfere with free-radical polymerization (e.g., polymerizable olefinic double bonds, thiols, and other such functionality known to those skilled in the art).
  • suitable linking groups X include straight chain, branched chain or cyclic alkylene, arylene or aralkylene groups, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, oxy, and combinations thereof such as sulfonamidoalkylene.
  • the fluorinated monomer is an ester of an ⁇ , ⁇ - ethylenically unsaturated carboxylic acid that can be represented by the general formula
  • R r X 1 -OC(O)-C(R 2 ) CH 2 (I) wherein R f represents a perfluorinated aliphatic group having 3 or 4 carbon atoms as described above, X 1 is an organic divalent linking group and R 2 represents hydrogen or a lower alkyl group having 1 to 4 carbon atoms. X 1 may for example be a hydrocarbon group that optionally may be substituted and/or that may contain oxygen, nitrogen or sulphur- containing groups or a combination thereof. Generally X 1 is an aliphatic group, e.g. an aliphatic group having between 1 and 10 carbon atoms.
  • the fluorinated monomer or mixture thereof is typically used in amounts such that the amount of the corresponding repeating units thereof in the fluorinated oligomer is at least 50 mole %, for example at least 55 mole %. In a particular embodiment, the amount of repeating units resulting from a fluorinated monomer may be at least 60 mole %.
  • the hydrocarbon monomer can be represented by the general formula : R h -E 2 (II) wherein R h represents hydrogen, Cl or a hydrocarbon group that may optionally contain one or more catenary or non-catenary heteroatoms and that may be contain one or more chlorine atoms and E 2 represents an ethylenically unsaturated group.
  • the hydrocarbon group R 1 is typically selected from the group consisting of a linear, branched or cyclic alkyl group, an aralkyl group, an alkylaryl group and an aryl group which may or may not be substituted with substituents such as e.g. oxyalkylene groups, hydroxy groups, amino groups or chlorine.
  • hydrocarbon monomers include esters of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid.
  • examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, octadecyl(meth)acrylate, lauryl(meth)acrylate, cyclohexyl (meth)acrylate, cyclodecyl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, adamantyl (meth)acrylate, tolyl (meth)acrylate, 3,3-dimethylbutyl (meth)acrylate, (2,2-dimethyl-l-methyl)propyl (meth)acrylate, cyclopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate
  • hydrocarbon monomers include allyl esters such as allyl acetate and allyl heptanoate; alkyl vinyl ethers or alkyl allyl ethers such as cetyl vinyl ether, dodecylvinyl ether, ethylvinyl ether; esters of unsaturated acids esters such as vinyl, allyl, methyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, cyclohexyl, lauryl, stearyl, isobornyl or alkoxy ethyl acrylates and methacrylates; alpha-beta unsaturated nitriles such as acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, alkyl cyanoacrylates; alpha,beta-unsaturated carboxylic acid derivatives such as allyl alcohol, allyl
  • hydrocarbon monomers that may be copolymerised with the fluorinated monomer include those selected from isobutyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, vinylidenechloride and octadecyl(meth)acrylate.
  • the hydrocarbon monomers can be used in amounts such that the amount of the corresponding units in the oligomer is less than 50 mole %, generally less than 40 mole %.
  • the fluorinated oligomer used in the invention can typically be prepared by free radical polymerisation in a solvent or mixture of solvents, in order to obtain repeating units derived from said fluorinated monomers and said hydrocarbon monomers.
  • suitable solvents include aliphatic and alicyclic hydrocarbons (e.g. hexane, heptane, cyclohexane, isoparaffin), aromatic solvents (e.g. benzene, toluene, xylene), ethers (e.g. diethylether, glyme, diglyme, diisopropylether), esters (e.g.
  • Halogenated solvents such as fluorinated solvents, e.g. HFE-7100 or HFE-7200 (available from 3M Company) can be used as co-solvents.
  • the reactants can be present in the solvent at any suitable concentration, e.g., from about 5 percent to about 90 percent by weight based on the total weight of the reaction mixture.
  • the mixture can be further diluted with an organic solvent or mixture of organic solvents to obtain the desired concentration.
  • the polymerisation can be a thermal or photochemical polymerisation, carried out in the presence of a free radical initiator.
  • a free radical initiator include azo compounds, such as azobisisobutyronitrile (AIBN), 2,2'-azo bis(2-methyl- butyronitrile) (V-59), azobisvaleronitrile and azobis(2-cyanovaleric acid), 2,2'-azobis(2- amidinopropane)dihydrochloride and the like, hydroperoxides such as cumene, t-butyl, and t-amyl hydroperoxide, dialkyl peroxides such as di-t-butyl and dicumylperoxide, peroxyesters such as t-butylperbenzoate and di-t-butylperoxy phtalate, diacylperoxides such as benzoyl peroxide and lauroyl peroxide.
  • AIBN azobisisobutyronitrile
  • Suitable chain transfer agents or chain terminators include mercapto compounds such as alkylmercaptans. Specific examples include butyl mercaptan, n-octyl mercaptan, 2-mercapto ethyl ether, 2- mercapto imidazole and octadecyl-3-mercaptopropionate. Fluorinated chain transfer agents such as a fluorinated mercapto compound can be used as well.
  • fluorinated chain transfer agent examples include those of the formula: (Rr 1 VQ-SH (HI) wherein R' f is a perfluorinated aliphatic group having 3 or 4 carbon atoms, n is 1 or 2, and wherein Q is an organic linking group such as an organic linking group described for X in respect of formula (I) above.
  • Rr 1 VQ-SH HI
  • R' f is a perfluorinated aliphatic group having 3 or 4 carbon atoms
  • n is 1 or 2
  • Q is an organic linking group such as an organic linking group described for X in respect of formula (I) above.
  • compounds according for formula (HI) include:
  • the amount of the chain transfer agent used should be chosen so as to obtain the desired molecular weight of the oligomer and will generally depend on the nature of the chain transfer agent and polymerization conditions used.
  • the chain transfer agent will typically be used in an amount between 0.25 and 25 mole % based on the fluorinated and non-fiuorinated monomers used.
  • the molecular weight of the fluorinated oligomer should be low in order to allow adequate penetration of the treatment solution into the porous stone.
  • the fluorinated oligomer useful in the present invention has a weight average molecular weight of not more than 70,000 g/mol, preferably not more than 50,000 g/mol.
  • the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is low, for example not more than 7, or not more than 5 or even not more than 3.
  • the molecular weight distribution may be between 1.5 and 5 although a molecular weight distribution outside this range and/or larger than 7 may be useful as well.
  • the amount of fluorinated oligomer useful in the treatment composition will typically be between 1 and 20 %, for example between 2 and 15 %, or between 3 and 10% by weight.
  • the composition used in the method of treatment further comprises an organic compound of an element M selected from the group consisting of Si, Ti, Zr, B, Pb, Sn, Zn and Al having at least two hydrolysable groups per molecule.
  • hydrolysable group in connection with the present invention refers to a group which either is directly capable of undergoing condensation reactions under appropriate conditions or which is capable of hydro lyzing under appropriate conditions, such as in the presence of water absorbed on and in the porous substrate.
  • the hydrolysable groups are directly bonded to the element M.
  • the fluorinated oligomer generally does not contain a silyl group having one or more hydrolysable groups or groups similar to a silyl group and capable of co-reacting with the organic compound of an element M, an improved treatment may be observed in connection with embodiments of this invention.
  • the compound of said element M can be represented by the formula wherein R 2 represents a non-hydrolysable group, M represents an element selected from the group consisting of Si, Ti, Zr, B, Pb, Sn, Zn and Al, p is 2, 3 or 4 depending on the valence of M, q is 0, 1 or 2, and Y 1 represents a hydrolysable group.
  • the hydrolysable groups may be the same or may be different.
  • the hydrolysable groups upon hydrolysis yield groups capable of undergoing condensation reactions, such as eg. silanol groups.
  • non-hydrolysable group refers to a group not capable of either directly undergoing condensation reactions under appropriate conditions or of hydrolysing under the conditions listed above for hydrolysing hydrolysable groups.
  • hydrolysable groups include halogens, such as chlorine, bromine, iodine or fluorine, alkoxy groups -OR' (wherein R' represents an alkyl group, preferably containing 1 to 8 carbon atoms and which may optionally be substituted by one or more halogen atoms), acyloxy groups -0(CO)-R" (wherein R" represents a lower alkyl group, preferably containing 1 to 6, more preferably 1 to 4 carbon atoms and which may optionally be substituted by one or more halogen atoms), aryloxy groups -OR'" (wherein R'" represents an aryl moiety, preferably containing 6 to 12, more preferably containing 6 to 10 carbon atoms, which may be optionally substituted by one or more substitu
  • halogens
  • hydrolysable groups include C 1 -C 8 alkoxy groups, such as methoxy, ethoxy, propoxy and isooctanolate groups ; chlorine and acetoxy groups.
  • Particularly preferred hydrolysable groups include C 1 -C 8 alkoxy groups, such as methoxy, ethoxy, and isooctanolate groups.
  • the non-hydrolysable groups R 2 may be the same or different and are generally not capable of hydrolyzing under the conditions listed above.
  • the non- hydrolysable groups R 2 may be independently selected from a hydrocarbon group, for example a Ci-C 30 alkyl group, which may be straight chain or branched and may include one or more aliphatic, cyclic hydrocarbon structures, a C 6 -C 30 aryl group (optionally substituted by one or more substituents selected from halogens and C 1 -C 4 alkyl groups), or a C 7 -C 3O aralkyl group.
  • a hydrocarbon group for example a Ci-C 30 alkyl group, which may be straight chain or branched and may include one or more aliphatic, cyclic hydrocarbon structures, a C 6 -C 30 aryl group (optionally substituted by one or more substituents selected from halogens and C 1 -C 4 alkyl groups), or a C 7 -C 3O
  • non-hydrolysable groups R 2 are independently selected from a hydrocarbon group, for example a Ci-C 30 alkyl group and a C 6 -C 20 aryl group (optionally substituted by one or more substituents selected from halogens and C 1 -C 4 alkyl groups).
  • Preferred compounds of element M include those in which M is Ti, Zr and Si.
  • Representative examples of compounds of element M include tetramethoxysilane, tetra ethoxysilane, methyl triethoxysilane, dimethyldiethoxysilane, octadecyltriethoxysilane, methyl trichlorosilane, tetra-methyl orthotitanate, tetra ethyl orthotitanate, tetra-iso-propyl orthotitanate, tetra-n-propyl orthotitanate, tetra-isooctyl orthotitanate, tetraethyl zirconate, tetra-iso-propyl zirconate, tetra-n-propyl zirconate and the like.
  • More preferred compounds include C 1 -C 8 alkoxy derivatives of Si, Ti and Zr.
  • Particularly preferred compounds of element M include dimethyldiethoxysilane, tetra-isooctyl orthotitanate and tetraethoxysilane. Single compounds or mixtures of compounds of element M may be used. Typically the compound of element M will be used in amounts between 0 and 500 parts by weight, more preferably between 5 and 200 parts by weight and most preferably between 10 and 100 parts by weight based on the weight of the fluorinated oligomer.
  • the fluorochemical composition may contain further additives, such as UV-light stabilisers, penetrants, viscosifiers, fillers, colorants and dyes.
  • additives such as UV-light stabilisers, penetrants, viscosifiers, fillers, colorants and dyes.
  • the treatment composition useful in the present invention comprises liquid.
  • the liquid comprises at least 70% by weight of an organic solvent based on the total amount of liquid.
  • the amount of organic solvent in the liquid is at least 75% by weight or in another embodiment is at least 80% by weight.
  • the fluorinated oligomer solution as obtained after the polymerization in a solvent as described above and the optional compound of element M may be diluted with an organic solvent to obtain the desired amounts of organic solvent and fluorinated oligomer in the composition.
  • Suitable organic solvents or mixtures of solvents include solvents useful for the polymerization of the fluorinated monomers and hydrocarbon monomers as given above.
  • the solvent or mixture of solvents should typically be chosen so as to obtain a fast drying treatment composition that has good penetration into the porous stone.
  • the organic solvent (or mixture) should have a boiling point of between 50°C and 200°C.
  • Solvents that are typically used include esters, such as ethylacetate, butylacetate or ethyleneglycol monobutyl ether acetate, ketones, such as acetone and methylethylketon, alcohols, such as isopropylalcohol and ethanol, ethers, such as propyleneglycol and dipropyleneglycolmonomethylether, methoxy2-propanol and hydrocarbon solvents, such as heptane or isoparaffin or mixtures thereof.
  • the method of the present invention can be used to treat porous stone.
  • porous stone include natural and man-made substrates such as for example marble, granite, terracotta, sandstone, concrete, limestone, porcelanico tiles and the like.
  • the method of the invention is contemplated as being particularly useful for imparting repellency properties to terracotta tiles, since these have very high water and oil absorption and may therefore be more susceptible to staining.
  • the composition comprising the fluorinated oligomer, the organic solvent and optional additives is chosen so as to obtain a treatment composition that can penetrate well into the porous stone.
  • the treatment solution will penetrate at least 1 mm, more preferably at least 5 mm into the porous stone.
  • the composition can be applied to the porous stone by brushing, spraying, dipping, immersing and the like. In one particular embodiment the composition isapplied using spraying.
  • the method of the present invention can be applied to the porous stone at ambient temperature (typically, about 2O 0 C to 35 0 C). Following application, the treated porous stone can be dried at a time sufficient to evaporate the solvent and at a temperature preferably not exceeding 80°C. Typically, the treated stone is dried at ambient temperature.
  • the amount of treatment composition to be applied to the porous stone will generally be that amount sufficient to provide the stone with desired water and/or oil repellency and/or soil resistance.
  • the amount should generally be selected such that contact angles with distilled water of at least 80° and a contact angle with n-hexadecane of at least 40 0 C, can be measured at 20 0 C.
  • the treatment is generally effective such that olive oil will not stain or penetrate the porous stone within a time period of 1 hour.
  • Treatment of porous stone generally results in rendering the stone less retentive of soil and readily cleanable. These desired properties may be maintained despite extended exposure of the porous stone to weather conditions or wearing of the porous stone during use.
  • the spray rating of a treated substrate is a value indicative of the dynamic repellency of the treated substrate to water that impinges on the treated substrate.
  • the repellency was measured by Standard Test Number 22, published in the 1985 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists (AATCC), and was expressed in terms of 'spray rating' of the tested substrate.
  • the spray rating was obtained by spraying 250 ml water on the substrate from a height of 15 cm.
  • the wetting pattern was visually rated using a 0 to 100 scale, where 0 meant complete wetting and 100 meant no wetting at all.
  • the treated substrates were tested for their contact angles versus water (W) and n-hexadecane (O) using an Olympus TGHM goniometer.
  • the contact angles were measured before (initial) and directly after abrasion (abrasion), unless otherwise indicated.
  • the values are the mean values of 4 measurements and are reported in degrees.
  • the minimum measurable value for a contact angle was 20°.
  • a value ⁇ 20° meant that the liquid spread on the surface.
  • the treated substrates were abraded using an AATCC Crockmeter, Model CMl available from Atlas Electric Company-USA,20 cycles using sandpaper nr. 600 (available from 3M).
  • MeFBSE(M)A N- methyl perfluoro-butyl sulfonamidoethyl (meth)acrylate
  • MeFOSEA N- methyl perfluoro-octyl sulfonamidoethyl acrylate
  • ISANETM IP- 175 Isoparaffin, available from Total Fina
  • EGMBA ethyleneglycol monobutyl ether acetate
  • BuAc butylacetate Tyzor TiOT : titanium tetra-isooctanolate, available from Du Pont de Nemours
  • Eosine red coloured antiseptic alcoholic solution, available from Wolfs, Belgium
  • Flaming red dye available from Fisher Scientific Co, USA, diluted in hexadecane at 2g/liter
  • Isobetadine commercially available, brown coloured antiseptic water based solution
  • Yellow oil Yellow Kurkuma dye dissolved in olive oil at 2% concentration
  • Fluorinated oligomer MeFBSEMA/ODMA (75/25) made with octadecyl-3- mercaptopropionate as chain transfer agent and further referred to as FC-I, was made according to the following procedure : A 500 ml glass bottle, equipped with a condenser, a temperature control and a dry N 2 inlet, was charged with 75 g MeFBSEMA (0.176 moles) followed by 25 g ODMA (0.073 moles) and 4.8 g (0.014 moles) octadecyl-S-mercaptopropionate. 70.6 g EGMBA was added and the reaction mixture was degassed 3 times under vacuum with dry N 2 .
  • V-59 catalyst was added (2% on solids) and the reaction temperature was increased to 75°C. The reaction was run for 20 hours under dry N 2 . After cooling to 30°C, additionally 0.25% V- 59 were added and the reaction mixture was heated to 75°C. The reaction was continued for 3 to 4 hours. The reaction mixture was cooled to 25°C and 3.54 g EGMBA and 173.05 g ISANETM IP- 175 were added. The mixture was stirred until it was homogeneous. The number and weight average molecular weight using GPC analysis were determined to be 4928 and 12209 respectively. . Treatment solutions were prepared by diluting the above prepared fluorinated oligomer solution to obtain 6 g fluorinated oligomer solids in 100 g butylacetate.
  • Fluorinated oligomer MeFBSEMA/ODMA (70/30), prepared with 5% by weight n- octylmercaptane as chain transfer agent (5g/100 g monomers) and further referred to as FC-2, was prepared according to the same procedure, but using butylacetate (reaction at 50% solids) as solvent. The number and weight average Mw, as determined by GPC were 3565 and 10481 respectively. Treatment solutions were prepared by diluting the above prepared fluorinated oligomer (6 g solids) in butylacetate (100 g).
  • Comparative fluoropolymer MeFBSEMA/ODMA 70/30
  • CFC-I Comparative fluoropolymer MeFBSEMA/ODMA
  • Comparative fluoropolymer CFC-2 was a waterbased fluorochemical acrylate, prepared according to US 6,037,429, example 1, but using MeFBSEA instead of MeFOSEA. The 20% concentrate was diluted to 6% solids in water.
  • Comparative fluoropolymer CFC-3 is a waterbased fluorochemical acrylate, prepared according to WO 01/36526, example 1. A 9% solids aqueous solution was obtained.
  • Comparative fluoropolymer CFC-4 was a waterbased fluorochemical acrylate, prepared according to US 6,120,892, example 1. The 30% concentrate was diluted to 6% solids in water.
  • Table 1 Oil and water repellency of terracotta tiles
  • terracotta tiles having a water absorption of about 10%, available from Ceramicas Calaf (Spain) were treated by spray application (at 2 bar at 150 ml/minute for about 30 sec) with fluorochemical compositions in BuAc, as given in table 2.
  • the treated tiles were allowed to dry at room temperature during 24 hours.
  • Comparative example C-I was made by spraying tiles with a 6% solution of comparative fluoropolymer CFC-I in butylacetate.
  • Comparative example C-2 was made with a 35% solution of FC-2 in butylacetate.
  • Comparative examples C-3 to C-5 were made using comparative fiuoropolymers CFC-2 to CFC-4 respectively.
  • the treated tiles were allowed to dry at room temperature during 24 hours.
  • Table 2 oil and water repellency of treated terracotta tiles

Abstract

The present invention relates to a method of treating porous stone, comprising contacting porous stone with a composition comprising: (i) a fluorinated oligomer having a weight average molecular weight of not more than 70,000 g/mol and comprising repeating units derived from one or more hydrocarbon monomers and one or more fluorinated monomers represented by the Formula (I): RfXt-E1 wherein Rf represents a perfluorinated aliphatic group having 3 or 4 carbon atoms, X represents a non-fluorinated organic linking group, t is 0 or 1 and E1 represents an ethylenically unsaturated group; and wherein the amount of repeating units derived from said fluorinated monomers is more than 50 mole % of the total amount of repeating units; (ii) a liquid dispersing or dissolving said fluorinated oligomer, said liquid comprising an organic solvent in an amount of at least 70% by weight based on the total amount of liquid; and wherein said fluorinated oligomer is contained in said composition in an amount of 1 to 20% by weight based on the total weight of the composition.

Description

METHOD FOR TREATING POROUS STONE USING A FLUOROCHEMICAL COMPOSITION
The present invention relates to a method of making porous stone water and oil repellent and stain resistant. The invention relates in particular to the use therein of a fluorinated oligomer that is based on repeating units of short chain fluorinated monomers and hydrocarbon monomers.
Porous stones are frequently used decoratively in the building industry and outdoor environment. When left unprotected, porous substrates, including porous stone, quickly loose their original appearance from exposure to water- and oil-based stains and gradually deteriorate from water penetration and weathering. Common household liquids are among the most severe stains, including motor oil, cooking oil and beverages, such as coffee and wine. In order to protect porous substrates from oil- and water-based stains, they are often sealed with a film-forming resin, such as an epoxy or urethane product. These coating materials are often quite expensive and may undesirably alter the appearance of the coated substrate. Such coatings also seal the product completely, preventing or greatly reducing the escape of moisture from the coated substrate.
Fluorochemical-containing treatments have been proposed to render porous substrates resistant to soil and repellent to water- and oil-based stains. For example, US 6,689,854 discloses a water-soluble and shelf-stable aqueous fluorochemical polymeric treatment useful to treat porous substrates to render them repellent to water- and oil-based stains. The treatment comprises a water-soluble or dispersible fluorochemical polymer containing only carbon atoms in the backbone, with a plurality of each of the following groups pendant from the backbone : (a) fluoroaliphatic groups, (b) carboxyl-containing groups, (c) silyl groups and optionally (d) other non-hydrophilic groups.
EP 1 225 187 discloses a fluorochemical composition comprising a major amount of an organic solvent and 0.05% by weight to 5% by weight of fluorochemical oligomer dispersed or dissolved in said organic solvent. The compositions are taught to be useful for rendering substrates, in particular ceramics or glass, water and/or oil repellent. US 4,366,300 discloses a compositon for protection of materials against contaminations, spots and stains. The liquid composition comprises by weight 0.1 to 1% of at least one fluorinated resin based on acrylic or methacrylic esters of fluorinated sulfonamido-alcohol, associated or not with non- fluorinated monomers, 0.4 to 10 % of at least one adjuvant selected from aminoplast resins based on melamine, thermoplastic resins and waxes, and 89 to 99.5% of at least one organic solvent.
Many surface treatments coat and seal the surface of the construction materials. This often results in an aesthetically undesirable shiny and unnatural appearance.
Additionally, such coating may cause a surface more slippery and prevent water drainage.
It would now be desirable to find an alternative treatment for providing porous stone, in particular terracotta, with high water repellency and/or high oil repellency. Desirably, such treatment is durable. Further desired properties include good stain resistance and/or stain release. Desirably, the treatment provides good repellency properties when applied at room temperature, dries fast and does not require curing at elevated temperatures. In particular, it would be desirable to find such treatment that can penetrate well into the porous surface of the stone and is highly effective without changing or undesirably diminishing the aesthetical appeal.
The present invention relates to a method of treating porous stone, comprising contacting porous stone with a composition comprising:
(i) a fluorinated oligomer having a weight average molecular weight of not more than 70,000 g/mol and comprising repeating units derived from one or more hydrocarbon monomers and one or more fluorinated monomers represented by the formula:
RrXt-E1 wherein Rf represents a perfluorinated aliphatic group having 3 or 4 carbon atoms, X represents a non-fluorinated organic linking group, t is 0 or 1 and E1 represents an ethylenically unsaturated group; and wherein the amount of repeating units derived from said fluorinated monomers is more than 50 mole % of the total amount of repeating units;
(ii) a liquid dispersing or dissolving said fluorinated oligomer, said liquid comprising an organic solvent in an amount of at least 70% by weight based on the total amount of liquid; and wherein said fluorinated oligomer is contained in said composition in an amount of 1 to 20% by weight based on the total weight of the composition.
It has been found that the method of the present invention may render porous stone water and/or oil repellent. The method may further provide stain repellency to the porous stone as well. The method is generally effective when applied at room temperature, generally shows good penetration. Typically, the treatment shows good durability, even without a heat treatment. The method may be particularly useful for providing terracotta tiles with desired properties including water repellency, oil repellency and stain resistance.
The fluorinated oligomers for use in the present invention comprise units derived from at least one hydrocarbon monomer and at least one fluorinated monomer and can be prepared by free-radical polymerization generally in the presence of a chain transfer agent. The fluorinated monomer can typically be represented by the formula : RrXt-E1 (I) wherein Rf represents a perfluorinated aliphatic group having 3 or 4 carbon atoms, X represents a non-fluorinated linking group, t is 0 or 1 and E1 represents an ethylenically unsaturated group.
The perfluorinated aliphatic group Rf is a perfluorinated, stable, inert, preferably saturated, non-polar, monovalent aliphatic radical containing 3 or 4 carbon atoms. It can be straight chain or branched chain. Especially suitable fluorinated monomers are those in which the Rf-group corresponds to the formula C4F9-. The linking group X, when present, links the perfluoroaliphatic group Rf to the ethylenically unsaturated group E1 and is generally a non-fluorinated organic linking group. The linking group X may be a hydrocarbon group which may optionally be substituted and which generally contains from 1 to about 20 carbon atoms. When X represents a hydrocarbon group, it may optionally contain oxygen, nitrogen, or sulfur- containing groups or a combination thereof, but X should typically be free of functional groups that substantially interfere with free-radical polymerization (e.g., polymerizable olefinic double bonds, thiols, and other such functionality known to those skilled in the art). Examples of suitable linking groups X include straight chain, branched chain or cyclic alkylene, arylene or aralkylene groups, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, oxy, and combinations thereof such as sulfonamidoalkylene.
In a particular embodiment the fluorinated monomer is an ester of an α,β- ethylenically unsaturated carboxylic acid that can be represented by the general formula
RrX1-OC(O)-C(R2)=CH2 (I) wherein Rf represents a perfluorinated aliphatic group having 3 or 4 carbon atoms as described above, X1 is an organic divalent linking group and R2 represents hydrogen or a lower alkyl group having 1 to 4 carbon atoms. X1 may for example be a hydrocarbon group that optionally may be substituted and/or that may contain oxygen, nitrogen or sulphur- containing groups or a combination thereof. Generally X1 is an aliphatic group, e.g. an aliphatic group having between 1 and 10 carbon atoms.
Specific examples of fluorinated monomers include: CF3CF2CF2CF2CH2CH2OCOCR1=CH2
CF3(CF2)3CH2OCOCR1-CH2
CF3(CF2)3SO2N(CH3)CH2CH2OCOCR'=CH2
CF3(CF2)3SO2N(C2H5)CH2CH2OCOCR1=CH2
CF3(CF2)3SO2N(CH3)CH2CH(CH3)OCOCR1=CH2 (CF3)2CFCF2SO2N(CH3)CH2CH2OCOCR1=CH2 wherein R1 is hydrogen or methyl. The fluorinated monomer or mixture thereof is typically used in amounts such that the amount of the corresponding repeating units thereof in the fluorinated oligomer is at least 50 mole %, for example at least 55 mole %. In a particular embodiment, the amount of repeating units resulting from a fluorinated monomer may be at least 60 mole %.
The hydrocarbon monomer can be represented by the general formula : Rh-E2 (II) wherein Rh represents hydrogen, Cl or a hydrocarbon group that may optionally contain one or more catenary or non-catenary heteroatoms and that may be contain one or more chlorine atoms and E2 represents an ethylenically unsaturated group.
The hydrocarbon group R1, is typically selected from the group consisting of a linear, branched or cyclic alkyl group, an aralkyl group, an alkylaryl group and an aryl group which may or may not be substituted with substituents such as e.g. oxyalkylene groups, hydroxy groups, amino groups or chlorine.
Examples of hydrocarbon monomers include esters of an α,β-ethylenically unsaturated carboxylic acid. Examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, octadecyl(meth)acrylate, lauryl(meth)acrylate, cyclohexyl (meth)acrylate, cyclodecyl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, adamantyl (meth)acrylate, tolyl (meth)acrylate, 3,3-dimethylbutyl (meth)acrylate, (2,2-dimethyl-l-methyl)propyl (meth)acrylate, cyclopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-butyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, 4-ethyl-cyclohexyl (meth)acrylate, 2- ethoxyethyl methacrylate, tetrahydropyranyl acrylate and vinyl and allyl (meth)acrylates. Further hydrocarbon monomers include allyl esters such as allyl acetate and allyl heptanoate; alkyl vinyl ethers or alkyl allyl ethers such as cetyl vinyl ether, dodecylvinyl ether, ethylvinyl ether; esters of unsaturated acids esters such as vinyl, allyl, methyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, cyclohexyl, lauryl, stearyl, isobornyl or alkoxy ethyl acrylates and methacrylates; alpha-beta unsaturated nitriles such as acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, alkyl cyanoacrylates; alpha,beta-unsaturated carboxylic acid derivatives such as allyl alcohol, allyl glycolate, acrylamide, methacrylamide, n-.diisopropyl acrylamide, diacetoneacrylamide, aminoalkyl (meth)acrylates such as N,N-diethylaminoethylmethacrylate, N-t- butylaminoethylmethacrylate; styrene and its derivatives such as vinyltoluene, alpha- methylstyrene, alpha-cyanomethyl styrene; lower olefinic hydrocarbons which can contain halogen such as ethylene, propylene, isobutene, 3-chloro-l-isobutene, butadiene, isoprene, chloro and dichlorobutadiene and 2,5-dimethyl-l,5-hexadiene. Further examples of non- fluorinated comonomers include chlorine containing comonomers such as vinyl chloride and vinylidene chloride.
In a particular embodiment the hydrocarbon monomers that may be copolymerised with the fluorinated monomer include those selected from isobutyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, vinylidenechloride and octadecyl(meth)acrylate.
The hydrocarbon monomers can be used in amounts such that the amount of the corresponding units in the oligomer is less than 50 mole %, generally less than 40 mole %.
The fluorinated oligomer used in the invention can typically be prepared by free radical polymerisation in a solvent or mixture of solvents, in order to obtain repeating units derived from said fluorinated monomers and said hydrocarbon monomers. Examples of suitable solvents include aliphatic and alicyclic hydrocarbons (e.g. hexane, heptane, cyclohexane, isoparaffin), aromatic solvents (e.g. benzene, toluene, xylene), ethers (e.g. diethylether, glyme, diglyme, diisopropylether), esters (e.g. ethyl acetate, butyl acetate, ethyleneglycol monobutyl ether acetate), alcohols (e.g. ethanol, isopropyl alcohol), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone), sulfoxides (e.g. dimethyl sulfoxide) and amides (e.g. N,N-dimethylformamide, N,N-dimethylacetamide). Halogenated solvents ,such as fluorinated solvents, e.g. HFE-7100 or HFE-7200 (available from 3M Company) can be used as co-solvents. The reactants can be present in the solvent at any suitable concentration, e.g., from about 5 percent to about 90 percent by weight based on the total weight of the reaction mixture. After polymerization, the mixture can be further diluted with an organic solvent or mixture of organic solvents to obtain the desired concentration.
The polymerisation can be a thermal or photochemical polymerisation, carried out in the presence of a free radical initiator. Useful free radical initiators are known in the art and include azo compounds, such as azobisisobutyronitrile (AIBN), 2,2'-azo bis(2-methyl- butyronitrile) (V-59), azobisvaleronitrile and azobis(2-cyanovaleric acid), 2,2'-azobis(2- amidinopropane)dihydrochloride and the like, hydroperoxides such as cumene, t-butyl, and t-amyl hydroperoxide, dialkyl peroxides such as di-t-butyl and dicumylperoxide, peroxyesters such as t-butylperbenzoate and di-t-butylperoxy phtalate, diacylperoxides such as benzoyl peroxide and lauroyl peroxide.
In order to obtain the desired molecular weight, the polymerisation is conveniently carried out in the presence of a chain transfer agent or a chain terminator. Suitable chain transfer agents or chain terminators include mercapto compounds such as alkylmercaptans. Specific examples include butyl mercaptan, n-octyl mercaptan, 2-mercapto ethyl ether, 2- mercapto imidazole and octadecyl-3-mercaptopropionate. Fluorinated chain transfer agents such as a fluorinated mercapto compound can be used as well. Examples of fluorinated chain transfer agent include those of the formula: (Rr1VQ-SH (HI) wherein R'f is a perfluorinated aliphatic group having 3 or 4 carbon atoms, n is 1 or 2, and wherein Q is an organic linking group such as an organic linking group described for X in respect of formula (I) above. Examples of compounds according for formula (HI) include:
C4F9SO2N(Me)CH2CH2OCOCH2CH2-SH, C4F9SO2N(Me)CH2CH2SH and C4F9SO2N(Me)CH2CH2OCOCH2CH(SH)-COO-CH2CH2N(Me)O2SC4F9. The amount of the chain transfer agent used should be chosen so as to obtain the desired molecular weight of the oligomer and will generally depend on the nature of the chain transfer agent and polymerization conditions used. The chain transfer agent will typically be used in an amount between 0.25 and 25 mole % based on the fluorinated and non-fiuorinated monomers used. The molecular weight of the fluorinated oligomer should be low in order to allow adequate penetration of the treatment solution into the porous stone. Typically the fluorinated oligomer useful in the present invention has a weight average molecular weight of not more than 70,000 g/mol, preferably not more than 50,000 g/mol. In a particular embodiment, the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is low, for example not more than 7, or not more than 5 or even not more than 3. Generallythe molecular weight distribution may be between 1.5 and 5 although a molecular weight distribution outside this range and/or larger than 7 may be useful as well. The amount of fluorinated oligomer useful in the treatment composition will typically be between 1 and 20 %, for example between 2 and 15 %, or between 3 and 10% by weight.
In one embodiment of the present invention the composition used in the method of treatment further comprises an organic compound of an element M selected from the group consisting of Si, Ti, Zr, B, Pb, Sn, Zn and Al having at least two hydrolysable groups per molecule. The term "hydrolysable group" in connection with the present invention refers to a group which either is directly capable of undergoing condensation reactions under appropriate conditions or which is capable of hydro lyzing under appropriate conditions, such as in the presence of water absorbed on and in the porous substrate. Preferably, the hydrolysable groups are directly bonded to the element M.
Notwithstanding the fact that the fluorinated oligomer generally does not contain a silyl group having one or more hydrolysable groups or groups similar to a silyl group and capable of co-reacting with the organic compound of an element M, an improved treatment may be observed in connection with embodiments of this invention.
In a particular embodiment of the present invention, the compound of said element M can be represented by the formula
Figure imgf000009_0001
wherein R2 represents a non-hydrolysable group, M represents an element selected from the group consisting of Si, Ti, Zr, B, Pb, Sn, Zn and Al, p is 2, 3 or 4 depending on the valence of M, q is 0, 1 or 2, and Y1 represents a hydrolysable group. The hydrolysable groups may be the same or may be different. Preferably, the hydrolysable groups upon hydrolysis yield groups capable of undergoing condensation reactions, such as eg. silanol groups. Accordingly, the term "non-hydrolysable group refers to a group not capable of either directly undergoing condensation reactions under appropriate conditions or of hydrolysing under the conditions listed above for hydrolysing hydrolysable groups. Examples of hydrolysable groups include halogens, such as chlorine, bromine, iodine or fluorine, alkoxy groups -OR' (wherein R' represents an alkyl group, preferably containing 1 to 8 carbon atoms and which may optionally be substituted by one or more halogen atoms), acyloxy groups -0(CO)-R" (wherein R" represents a lower alkyl group, preferably containing 1 to 6, more preferably 1 to 4 carbon atoms and which may optionally be substituted by one or more halogen atoms), aryloxy groups -OR'" (wherein R'" represents an aryl moiety, preferably containing 6 to 12, more preferably containing 6 to 10 carbon atoms, which may be optionally substituted by one or more substituents independently selected from halogens, and C1-C4 alkyl groups which may optionally be substituted by one or more halogen atoms). In the above formulae R', R", and R'" may include linear, branched and/or cyclic structures.
Specific examples of hydrolysable groups include C1-C8 alkoxy groups, such as methoxy, ethoxy, propoxy and isooctanolate groups ; chlorine and acetoxy groups. Particularly preferred hydrolysable groups include C1-C8 alkoxy groups, such as methoxy, ethoxy, and isooctanolate groups.
The non-hydrolysable groups R2 may be the same or different and are generally not capable of hydrolyzing under the conditions listed above. For example, the non- hydrolysable groups R2 may be independently selected from a hydrocarbon group, for example a Ci-C30 alkyl group, which may be straight chain or branched and may include one or more aliphatic, cyclic hydrocarbon structures, a C6-C30 aryl group (optionally substituted by one or more substituents selected from halogens and C1-C4 alkyl groups), or a C7-C3O aralkyl group. In one embodiment the non-hydrolysable groups R2 are independently selected from a hydrocarbon group, for example a Ci-C30 alkyl group and a C6-C20 aryl group (optionally substituted by one or more substituents selected from halogens and C1-C4 alkyl groups).
Preferred compounds of element M include those in which M is Ti, Zr and Si. Representative examples of compounds of element M include tetramethoxysilane, tetra ethoxysilane, methyl triethoxysilane, dimethyldiethoxysilane, octadecyltriethoxysilane, methyl trichlorosilane, tetra-methyl orthotitanate, tetra ethyl orthotitanate, tetra-iso-propyl orthotitanate, tetra-n-propyl orthotitanate, tetra-isooctyl orthotitanate, tetraethyl zirconate, tetra-iso-propyl zirconate, tetra-n-propyl zirconate and the like. More preferred compounds include C1-C8 alkoxy derivatives of Si, Ti and Zr. Particularly preferred compounds of element M include dimethyldiethoxysilane, tetra-isooctyl orthotitanate and tetraethoxysilane. Single compounds or mixtures of compounds of element M may be used. Typically the compound of element M will be used in amounts between 0 and 500 parts by weight, more preferably between 5 and 200 parts by weight and most preferably between 10 and 100 parts by weight based on the weight of the fluorinated oligomer.
The fluorochemical composition may contain further additives, such as UV-light stabilisers, penetrants, viscosifiers, fillers, colorants and dyes.
The treatment composition useful in the present invention comprises liquid. The liquid comprises at least 70% by weight of an organic solvent based on the total amount of liquid. In a particular embodiment, the amount of organic solvent in the liquid is at least 75% by weight or in another embodiment is at least 80% by weight. Thus the fluorinated oligomer solution as obtained after the polymerization in a solvent as described above and the optional compound of element M may be diluted with an organic solvent to obtain the desired amounts of organic solvent and fluorinated oligomer in the composition. Suitable organic solvents or mixtures of solvents include solvents useful for the polymerization of the fluorinated monomers and hydrocarbon monomers as given above. The solvent or mixture of solvents should typically be chosen so as to obtain a fast drying treatment composition that has good penetration into the porous stone. Typically the organic solvent (or mixture) should have a boiling point of between 50°C and 200°C. Solvents that are typically used include esters, such as ethylacetate, butylacetate or ethyleneglycol monobutyl ether acetate, ketones, such as acetone and methylethylketon, alcohols, such as isopropylalcohol and ethanol, ethers, such as propyleneglycol and dipropyleneglycolmonomethylether, methoxy2-propanol and hydrocarbon solvents, such as heptane or isoparaffin or mixtures thereof.
The method of the present invention can be used to treat porous stone. Examples of porous stone include natural and man-made substrates such as for example marble, granite, terracotta, sandstone, concrete, limestone, porcelanico tiles and the like. The method of the invention is contemplated as being particularly useful for imparting repellency properties to terracotta tiles, since these have very high water and oil absorption and may therefore be more susceptible to staining.
The composition comprising the fluorinated oligomer, the organic solvent and optional additives is chosen so as to obtain a treatment composition that can penetrate well into the porous stone. Preferably the treatment solution will penetrate at least 1 mm, more preferably at least 5 mm into the porous stone. The composition can be applied to the porous stone by brushing, spraying, dipping, immersing and the like. In one particular embodiment the composition isapplied using spraying. The method of the present invention can be applied to the porous stone at ambient temperature (typically, about 2O0C to 350C). Following application, the treated porous stone can be dried at a time sufficient to evaporate the solvent and at a temperature preferably not exceeding 80°C. Typically, the treated stone is dried at ambient temperature.
The amount of treatment composition to be applied to the porous stone will generally be that amount sufficient to provide the stone with desired water and/or oil repellency and/or soil resistance. The amount should generally be selected such that contact angles with distilled water of at least 80° and a contact angle with n-hexadecane of at least 400C, can be measured at 200C. The treatment is generally effective such that olive oil will not stain or penetrate the porous stone within a time period of 1 hour. Treatment of porous stone generally results in rendering the stone less retentive of soil and readily cleanable. These desired properties may be maintained despite extended exposure of the porous stone to weather conditions or wearing of the porous stone during use.
EXAMPLES
The following examples further illustrate the invention without the intention however to limit the invention thereto. All parts are by weight unless indicated otherwise.
Respective data of water and oil repellency shown in the following Examples and Comparative Examples are based on the following method of measurement and evaluation criteria:
Spray Rating (SR) The spray rating of a treated substrate is a value indicative of the dynamic repellency of the treated substrate to water that impinges on the treated substrate. The repellency was measured by Standard Test Number 22, published in the 1985 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists (AATCC), and was expressed in terms of 'spray rating' of the tested substrate. The spray rating was obtained by spraying 250 ml water on the substrate from a height of 15 cm. The wetting pattern was visually rated using a 0 to 100 scale, where 0 meant complete wetting and 100 meant no wetting at all.
Contact Angles The treated substrates were tested for their contact angles versus water (W) and n-hexadecane (O) using an Olympus TGHM goniometer. The contact angles were measured before (initial) and directly after abrasion (abrasion), unless otherwise indicated. The values are the mean values of 4 measurements and are reported in degrees. The minimum measurable value for a contact angle was 20°. A value <20° meant that the liquid spread on the surface. The treated substrates were abraded using an AATCC Crockmeter, Model CMl available from Atlas Electric Company-USA,20 cycles using sandpaper nr. 600 (available from 3M).
Abbreviations
MeFBSE(M)A: N- methyl perfluoro-butyl sulfonamidoethyl (meth)acrylate
MeFOSEA: N- methyl perfluoro-octyl sulfonamidoethyl acrylate
ODMA : octadecyl methacrylate FC : fluorochemical
ISANE™ IP- 175 : Isoparaffin, available from Total Fina
EGMBA : ethyleneglycol monobutyl ether acetate
V-59 : 2,2'azobis (2-methyl-butyronitrile) obtained from Wako
BuAc : butylacetate Tyzor TiOT : titanium tetra-isooctanolate, available from Du Pont de Nemours
Eosine : red coloured antiseptic alcoholic solution, available from Wolfs, Belgium
Red oil : Flaming red dye, available from Fisher Scientific Co, USA, diluted in hexadecane at 2g/liter
Isobetadine : commercially available, brown coloured antiseptic water based solution Yellow oil : Yellow Kurkuma dye dissolved in olive oil at 2% concentration
Red wine : Cόtes du Roussillon Village, France
Coffee : 20g/liter Nescafe powder
Synthesis of fluorinated oligomers comparative fluoropolvmers
Fluorinated oligomer MeFBSEMA/ODMA (75/25) made with octadecyl-3- mercaptopropionate as chain transfer agent and further referred to as FC-I, was made according to the following procedure : A 500 ml glass bottle, equipped with a condenser, a temperature control and a dry N2 inlet, was charged with 75 g MeFBSEMA (0.176 moles) followed by 25 g ODMA (0.073 moles) and 4.8 g (0.014 moles) octadecyl-S-mercaptopropionate. 70.6 g EGMBA was added and the reaction mixture was degassed 3 times under vacuum with dry N2. V-59 catalyst was added (2% on solids) and the reaction temperature was increased to 75°C. The reaction was run for 20 hours under dry N2. After cooling to 30°C, additionally 0.25% V- 59 were added and the reaction mixture was heated to 75°C. The reaction was continued for 3 to 4 hours. The reaction mixture was cooled to 25°C and 3.54 g EGMBA and 173.05 g ISANE™ IP- 175 were added. The mixture was stirred until it was homogeneous. The number and weight average molecular weight using GPC analysis were determined to be 4928 and 12209 respectively. . Treatment solutions were prepared by diluting the above prepared fluorinated oligomer solution to obtain 6 g fluorinated oligomer solids in 100 g butylacetate.
Fluorinated oligomer MeFBSEMA/ODMA (70/30), prepared with 5% by weight n- octylmercaptane as chain transfer agent (5g/100 g monomers) and further referred to as FC-2, was prepared according to the same procedure, but using butylacetate (reaction at 50% solids) as solvent. The number and weight average Mw, as determined by GPC were 3565 and 10481 respectively. Treatment solutions were prepared by diluting the above prepared fluorinated oligomer (6 g solids) in butylacetate (100 g).
Comparative fluoropolymer MeFBSEMA/ODMA (70/30), prepared without the addition of chain transfer agent, and further referred to as CFC-I, was prepared according to the same procedure in butylacetate at 50% solids. GPC analysis indicated that the number and weight average Mw of the polymer were 40272 and 93620 respectively.
Comparative fluoropolymer CFC-2 was a waterbased fluorochemical acrylate, prepared according to US 6,037,429, example 1, but using MeFBSEA instead of MeFOSEA. The 20% concentrate was diluted to 6% solids in water. Comparative fluoropolymer CFC-3 is a waterbased fluorochemical acrylate, prepared according to WO 01/36526, example 1. A 9% solids aqueous solution was obtained. Comparative fluoropolymer CFC-4 was a waterbased fluorochemical acrylate, prepared according to US 6,120,892, example 1. The 30% concentrate was diluted to 6% solids in water.
Examples 1 to 6
In examples 1 to 6, 30x15 cm2 terracotta tiles, available from Butech (Spain), having a water absorption of about 15%, were treated with the fluorochemical solutions as given in table 1, by spray application at 2 bar at 150 ml/minute for about 30 sec. Treated tiles were allowed to dry for 24 hours at room temperature. No heat treatment was applied. After drying, the treated tiles were tested for their contact angles versus water (W) and n- hexadecane (O) using an Olympus TGHM goniometer. The treated tiles were tested for their water repellency using the spray rating test. The results are given in table 1.
Table 1 : Oil and water repellency of terracotta tiles
Figure imgf000016_0001
Untreated tiles gave no repellency to water and n-hexadecane (contact angles <20° and SR =0).
Examples 7 to 9 and comparative examples C-I to C-5
In examples 7 to 9, terracotta tiles, having a water absorption of about 10%, available from Ceramicas Calaf (Spain) were treated by spray application (at 2 bar at 150 ml/minute for about 30 sec) with fluorochemical compositions in BuAc, as given in table 2. The treated tiles were allowed to dry at room temperature during 24 hours. Comparative example C-I was made by spraying tiles with a 6% solution of comparative fluoropolymer CFC-I in butylacetate. Comparative example C-2 was made with a 35% solution of FC-2 in butylacetate. Comparative examples C-3 to C-5 were made using comparative fiuoropolymers CFC-2 to CFC-4 respectively. The treated tiles were allowed to dry at room temperature during 24 hours. After drying, the tiles were evaluated for their oil and water repellency initially and after abrasion. The results are given in table 2. The tiles were tested for their stain repellency properties by applying different stains. The stains were left on the treated tiles for 16 hours at room temperature. The residues were cleaned off using a paper wipe and the tiles were visually inspected and rated using a scale from 1 to 5 (1 means no stain visible ; 5 means severe stain). The results are summarized in table 3.
Table 2 : oil and water repellency of treated terracotta tiles
Figure imgf000017_0001
NA : not available Table 3 : Stain repellency of terracotta tiles treated with fluorochemical compositions
Figure imgf000018_0001

Claims

1. Method of treatment comprising contacting porous stone with a composition comprising: (i) a fiuorinated oligomer having a weight average molecular weight of not more than 70,000 g/mol and comprising repeating units derived from one or more hydrocarbon monomers and one or more fiuorinated monomers represented by the formula: RfXt-E1 wherein Rf represents a perfluorinated aliphatic group having 3 or 4 carbon atoms, X represents a non-fluorinated linking group, t is 0 or 1 and E1 represents an ethylenically unsaturated group; and wherein the amount of repeating units derived from said fiuorinated monomers is more than 50 mole % of the total amount of repeating units; (ii) a liquid dispersing or dissolving said fiuorinated oligomer, said liquid comprising an organic solvent in an amount of at least 70% by weight based on the total amount of liquid; and wherein said fiuorinated oligomer is contained in said composition in an amount of 1 to 20% by weight based on the total weight of the composition.
2. Method according to claim 1 wherein said composition further comprises an organic compound of an element M selected from the group consisting of Si, Ti, Zr, B, Pb, Sn, Zn and Al and having at least two hydrolysable groups per molecule.
3. Method according to claim 2 wherein said compound of said element M corresponds to the formula:
Figure imgf000019_0001
wherein R2 represents a non-hydrolysable group, M has the same meaning as defined in claim 2, Y1 represents a hydrolysable group, p is 2, 3 or 4 and corresponds to the valence of M and q is 0, 1 or 2 and p-q is at least 2.
4. Method according to claim 2 or 3 wherein M is selected from Si, Ti or Zr.
5. Method according to any of claims 2 to 4 wherein said organic compound is present in an amount of 10 to 100 parts by weight based on the weight of said fluorinated oligomer.
6. Method according to any of the previous claims wherein said liquid comprises organic solvent in an amount of at least 80% by weight.
7. Method according to any of the previous claims wherein said fluorinated oligomer is contained in said composition in an amount of 2 to 15% by weight.
8. Method according to any of the previous claims wherein said hydrocarbon monomers correspond to the general formula: Rh-E2 wherein E2 represents an ethylenically unsaturated group and wherein Rh represents hydrogen, Cl or a hydrocarbon group that may optionally contain one or more catenary or non-catenary heteroatoms.
9. Method according to any of the previous claims wherein said fluorinated oligomer consists of repeating units derived from said fluorinated monomers and said hydrocarbon monomers.
10. Method according to any of the previous claims wherein said porous stone is selected from marble, granite, terracotta and concrete.
11. Method according to any of the previous claims wherein said composition is applied to said porous stone in amount sufficient to provide oil- and water repellency to said porous stone.
12. Method according to any of the previous claims wherein said organic solvent is selected from ketones, esters, alcohols, hydrocarbons and ethers.
13. Method according to any of the previous claims wherein said organic solvent has a boiling point between 50°C and 200°C.
14. Method according to any of the previous claims wherein said porous stone is contacted with said composition at a temperature of not more than 80°C and allowed to dry at a temperature of not more than 80°C.
PCT/US2005/026810 2004-09-02 2005-07-29 Method for treating porous stone using a fluorochemical composition WO2006028608A1 (en)

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BRPI0514854-5A BRPI0514854A (en) 2004-09-02 2005-07-29 porous stone treatment method
CA002579163A CA2579163A1 (en) 2004-09-02 2005-07-29 Method for treating porous stone using a fluorochemical composition
AU2005283038A AU2005283038A1 (en) 2004-09-02 2005-07-29 Method for treating porous stone using a fluorochemical composition
CN2005800348803A CN101039888B (en) 2004-09-02 2005-07-29 Method for treating porous stone using a fluorochemical composition
MX2007002628A MX2007002628A (en) 2004-09-02 2005-07-29 Method for treating porous stone using a fluorochemical composition.

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EP04104235A EP1632464B1 (en) 2004-09-02 2004-09-02 Method for treating porous stone using a fluorochemical composition

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7585817B2 (en) 2006-08-23 2009-09-08 Board Of Regents, The University Of Texas System Compositions and methods for improving the productivity of hydrocarbon producing wells using a non-ionic fluorinated polymeric surfactant
US7772162B2 (en) 2006-03-27 2010-08-10 Board Of Regents, The University Of Texas System Use of fluorocarbon surfactants to improve the productivity of gas and gas condensate wells
US8043998B2 (en) 2007-03-23 2011-10-25 Board Of Regents, The University Of Texas System Method for treating a fractured formation with a non-ionic fluorinated polymeric surfactant
US8138127B2 (en) 2007-03-23 2012-03-20 Board Of Regents, The University Of Texas Compositions and methods for treating a water blocked well using a nonionic fluorinated surfactant
US8261825B2 (en) 2007-11-30 2012-09-11 Board Of Regents, The University Of Texas System Methods for improving the productivity of oil producing wells
US8403050B2 (en) 2007-03-23 2013-03-26 3M Innovative Properties Company Method for treating a hydrocarbon-bearing formation with a fluid followed by a nonionic fluorinated polymeric surfactant
ITFI20120131A1 (en) * 2012-06-22 2013-12-23 Benelli S R L COMPOSITION AND WATERPROOFING TREATMENT
US9353309B2 (en) 2007-03-23 2016-05-31 Board Of Regents, The University Of Texas System Method for treating a formation with a solvent

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001030873A1 (en) 1999-10-27 2001-05-03 3M Innovative Properties Company Fluorochemical sulfonamide surfactants
US7629298B2 (en) * 2006-02-21 2009-12-08 3M Innovative Properties Company Sandstone having a modified wettability and a method for modifying the surface energy of sandstone
WO2008089386A2 (en) * 2007-01-19 2008-07-24 3M Innovative Properties Company Methods of using stable hydrocarbon foams
JP2010516451A (en) * 2007-01-19 2010-05-20 スリーエム イノベイティブ プロパティズ カンパニー Fluorinated surfactant and method of using the same
US20100025038A1 (en) * 2007-01-19 2010-02-04 Savu Patricia M Methods of using stable hydrocarbon foams
CN101679569A (en) * 2007-06-06 2010-03-24 3M创新有限公司 Fluorinated ether compositions and methods of using the same
CN101945971A (en) * 2007-12-21 2011-01-12 3M创新有限公司 Utilize the method for fluorinated polymer compositions-treated hydrocarbon containing formation
WO2009085936A1 (en) * 2007-12-21 2009-07-09 3M Innovative Properties Company Fluorinated polymer compositions and methods for treating hydrocarbon-bearing formations using the same
WO2009137285A1 (en) 2008-05-05 2009-11-12 3M Innovative Properties Company Methods for treating hydrocarbon-bearing formations having brine
US9200102B2 (en) * 2008-07-18 2015-12-01 3M Innovative Properties Company Cationic fluorinated polymer compositions and methods for treating hydrocarbon-bearing formations 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
MX2011006673A (en) 2008-12-18 2011-07-20 3M Innovative Properties Co Method of contacting hydrocarbon-bearing formations with fluorinated phosphate and phosphonate compositions.
US20110052874A1 (en) * 2009-07-02 2011-03-03 Wensheng Zhou Roofing articles with highly reflective coated granules
MX2012000413A (en) 2009-07-09 2012-02-08 3M Innovative Prosperties Company Methods for treating carbonate hydrocarbon-bearing formations with fluorinated amphoteric compounds.
WO2011082374A1 (en) 2009-12-31 2011-07-07 Firestone Building Products Company, Llc Asphaltic membrane with mullite-containing granules
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.
EP2663608A4 (en) 2011-01-13 2014-07-09 3M Innovative Properties Co Methods for treating siliciclastic hydrocarbon-bearing formations with fluorinated amine oxides
BR112015011484A2 (en) 2012-11-19 2017-07-11 3M Innovative Properties Co method for bringing hydrocarbon carrier formations into contact with fluorinated ion polymers
US9890294B2 (en) 2012-11-19 2018-02-13 3M Innovative Properties Company Composition including a fluorinated polymer and a non-fluorinated polymer and methods of making and using the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478975A (en) * 1983-01-28 1984-10-23 Atochem Compositions and process for the oilproofing and waterproofing treatment of construction materials
US6037429A (en) * 1995-06-16 2000-03-14 3M Innovative Properties Company Water-soluble fluorochemical polymers for use in water and oil repellent masonry treatments
EP1225187A1 (en) * 2001-01-19 2002-07-24 3M Innovative Properties Company Fluorovinyl oligomer component having silane groups, liquid compositions thereof and method of coating

Family Cites Families (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803615A (en) 1956-01-23 1957-08-20 Minnesota Mining & Mfg Fluorocarbon acrylate and methacrylate esters and polymers
US3787351A (en) 1972-02-28 1974-01-22 Minnesota Mining & Mfg Use of soluble fluoroaliphatic oligomers in resin composite articles
DE2526287C2 (en) * 1975-06-12 1982-09-30 Wacker-Chemie GmbH, 8000 München Process for making open porosity surfaces of normally solid inorganic materials repellant to oil and water
FR2483447A1 (en) 1980-06-03 1981-12-04 Ugine Kuhlmann COMPOSITION AND METHOD FOR PROTECTING MATERIALS AGAINST SOIL
US4557837A (en) 1980-09-15 1985-12-10 Minnesota Mining And Manufacturing Company Simulation and cleanup of oil- and/or gas-producing wells
IT1207493B (en) 1985-02-22 1989-05-25 Montefuols S P A E Franco Piac PROCEDURE FOR THE PROTECTION AND CONSOLIDATION OF STONE MATERIALS
US5276175A (en) 1991-04-02 1994-01-04 Minnesota Mining And Manufacturing Company Isocyanate derivatives comprising flourochemical oligomers
CA2090302A1 (en) 1992-03-20 1993-09-21 Larry D. Rich Aqueous dispersable oil and water repellent silane masonry penetrants
EP0624710A1 (en) 1993-05-05 1994-11-17 Minnesota Mining And Manufacturing Company A foamable oil well-treatment-fluid
FR2727417B1 (en) 1994-11-29 1997-01-03 Atochem Elf Sa CATIONIC FLUORINE COPOLYMERS FOR OLEOPHOBIC AND HYDROPHOBIC TREATMENT OF CONSTRUCTION MATERIALS
DE19610111A1 (en) 1996-03-14 1997-09-18 Wacker Chemie Gmbh Compositions for the water and oil repellent treatment of absorbent materials
TW377370B (en) 1996-04-12 1999-12-21 Du Pont Waterborne fluoropolymer solutions for treating hard surfaces
DE19634500A1 (en) 1996-08-26 1998-03-05 Wacker Chemie Gmbh Compositions for the water and oil repellent treatment of absorbent materials
US5989698A (en) 1997-02-10 1999-11-23 3M Innovative Properties Company Coated porous materials
US6120892A (en) 1997-11-20 2000-09-19 E. I. Du Pont De Nemours And Company Waterborne fluoropolymer solutions for treating hard surfaces
US6383569B2 (en) 1998-07-24 2002-05-07 Ciba Specialty Chemicals Corporation Compositions and methods to protect calcitic and/or siliceous materials
JP2002521299A (en) 1998-07-24 2002-07-16 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド Compositions and methods for protecting calcite and / or siliceous surfaces
WO2001030873A1 (en) 1999-10-27 2001-05-03 3M Innovative Properties Company Fluorochemical sulfonamide surfactants
US6271289B1 (en) 1999-11-16 2001-08-07 E. I. Du Pont De Nemours And Company Stain resistant compositions
EP1238004B1 (en) 1999-11-16 2004-01-28 E.I. du Pont de Nemours and Company Stain resistant compositions
WO2002004383A1 (en) 2000-07-07 2002-01-17 E.I. Dupont De Nemours And Company A method for protection of stone with substantially amorphous fluoropolymers
AU2001273428A1 (en) 2000-08-14 2002-02-25 3M Innovative Properties Company Urethane-based stain-release coatings
US6646088B2 (en) 2000-08-16 2003-11-11 3M Innovative Properties Company Urethane-based stain-release coatings
DE10049153A1 (en) 2000-09-27 2002-04-11 Degussa Paint, varnish, pollutants, bioorganisms, oil, water, and / or dirt-repellent coating
ES2282186T3 (en) 2001-01-19 2007-10-16 3M Innovative Properties Company FLUOROCHEMICAL SILANOS WATER SOLUBLE OR WATER DISPERSABLE TO MAKE A SUBSTRATE REPELLENT TO OIL AND WATER.
US6656258B2 (en) * 2001-03-20 2003-12-02 3M Innovative Properties Company Compositions comprising fluorinated silanes and compressed fluid CO2
US6689854B2 (en) 2001-08-23 2004-02-10 3M Innovative Properties Company Water and oil repellent masonry treatments
EP1329548A1 (en) 2002-01-21 2003-07-23 3M Innovative Properties Company Method of treatment of a textile or non-woven substrate to render same water and oil repellent
PT1369453E (en) 2002-06-03 2007-03-30 3M Innovative Properties Co Fluoro-silane-oligomer composition
US7041727B2 (en) 2002-06-25 2006-05-09 3M Innovative Properties Company Latex paint compositions and coatings
US6903173B2 (en) 2002-08-02 2005-06-07 3M Innovative Properties Co. Fluorinated polymers
EP1493761A1 (en) 2003-07-02 2005-01-05 3M Innovative Properties Company Fluoropolymer of fluorinated short chain acrylates or methacrylates and oil- and water repellent compositions based thereon
US7727710B2 (en) 2003-12-24 2010-06-01 3M Innovative Properties Company Materials, methods, and kits for reducing nonspecific binding of molecules to a surface

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478975A (en) * 1983-01-28 1984-10-23 Atochem Compositions and process for the oilproofing and waterproofing treatment of construction materials
US6037429A (en) * 1995-06-16 2000-03-14 3M Innovative Properties Company Water-soluble fluorochemical polymers for use in water and oil repellent masonry treatments
EP1225187A1 (en) * 2001-01-19 2002-07-24 3M Innovative Properties Company Fluorovinyl oligomer component having silane groups, liquid compositions thereof and method of coating

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7772162B2 (en) 2006-03-27 2010-08-10 Board Of Regents, The University Of Texas System Use of fluorocarbon surfactants to improve the productivity of gas and gas condensate wells
US7855169B2 (en) 2006-03-27 2010-12-21 Board Of Regents, The University Of Texas System Use of fluorocarbon surfactants to improve the productivity of gas and gas condensate wells
US7585817B2 (en) 2006-08-23 2009-09-08 Board Of Regents, The University Of Texas System Compositions and methods for improving the productivity of hydrocarbon producing wells using a non-ionic fluorinated polymeric surfactant
US8043998B2 (en) 2007-03-23 2011-10-25 Board Of Regents, The University Of Texas System Method for treating a fractured formation with a non-ionic fluorinated polymeric surfactant
US8138127B2 (en) 2007-03-23 2012-03-20 Board Of Regents, The University Of Texas Compositions and methods for treating a water blocked well using a nonionic fluorinated surfactant
US8403050B2 (en) 2007-03-23 2013-03-26 3M Innovative Properties Company Method for treating a hydrocarbon-bearing formation with a fluid followed by a nonionic fluorinated polymeric surfactant
US9353309B2 (en) 2007-03-23 2016-05-31 Board Of Regents, The University Of Texas System Method for treating a formation with a solvent
US8261825B2 (en) 2007-11-30 2012-09-11 Board Of Regents, The University Of Texas System Methods for improving the productivity of oil producing wells
ITFI20120131A1 (en) * 2012-06-22 2013-12-23 Benelli S R L COMPOSITION AND WATERPROOFING TREATMENT

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MX2007002628A (en) 2007-05-15
RU2007107857A (en) 2008-10-10
CN101039888B (en) 2010-06-16
ATE505447T1 (en) 2011-04-15
AU2005283038A1 (en) 2006-03-16
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CA2579163A1 (en) 2006-03-16

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