CA2222139A1 - Water and oil repellent masonry treatments - Google Patents

Abstract

The present invention provides 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 fluorochemical polymer containing only carbon atoms in the backbone, with a plurality of each of the following groups pendent from the backbone:
(a) fluoroaliphatic groups, (b) carboxyl-containing groups, (c) oxyalkylene or polyoxyalkylene groups, and, optionally, (d) silyl groups. Typically, the treatment polymers have interpolymerized units derived from one or more, and preferably a plurality, of each of the following monomers: (a) monomer selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, thioacrylate or meththioacrylate compounds containing a fluoroaliphatic moiety that is linked to the residue of the compound through a divalent, organic linking group; (b) monomer selected from the group consisting of acrylic acid, methacrylic acid, carboxyalkylacrylate and carboxyalkylmethacrylate compounds; and (c) monomer selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, thioacrylate or meththioacrylate compounds containing an oxyalkylene or polyoxyalkylene group linked to the residue of the compound through an oxygen, sulfur or nitrogen atom. Preferably, the polymer further includes interpolymerized units derived from monomers selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, thioacrylate and meththioacrylate compounds that contain an alkoxysilane moiety linked to the residue of the monomer through a divalent organic group. In another aspect, the present invention provides shelf-stable aqueous solutions or dispersions comprising the polymeric treatment and a method of treating porous substrates to render them repellent to water- and oil-based stains using the aforementioned polymeric product. Because the water-soluble polymeric treatment of the present invention, and the shelf-stable aqueous solutions thereof, can be applied to porous substrates in aqueous solution, they eliminate the need for environmentally harmful and toxic co-solvents. Particularly when applied to masonry and other siliceous materials, these polymeric treatments can react with the substrate onto which they are applied to form an invisible and water-insoluble coating that repels both water and oil, resists soiling, and that cannot be easily washed from the surface of the substrate. Substrates treated with these polymers are thereby durably protected from rain and normal weathering.

Description

CA 02222139 1997-11-2~
W O 97/00230 PC~AJS96/06313 Water and Oil Repellent Masonry Tr~ - ts FIELD OF 1 ~E INVENTION

This invention relates to water-soluble, soil~ and water and oil repellent fluorochemical polymers. More particularly, the present invention relates to the l,e~ of -"asoluy and other porous substrates with water-soluble fluorochemical polymers to render them re;,;sld.,t to soil and repellent to water- and oil-based stains.

BACKGROUND OF TEIE INVENTION

Masonry, a term used generically to describe building materials such as concrete, asphalt, brick, tile, stone, grout, and like subst~nces, is used extensively in the construction of b~ ing~, roads, parking ramps, driveways, garage flooring, firepl~ces, fireplace hearths, and counter tops. When left unprotected, masonry surfaces quickly discolor from exposure to water- and oil-based stains and gradually deteriorate from spalling and efflor~sc~n~e indnced by water pelleL"llion and weather exposure. Common household liquids are among the most severely discoloring stains inrlllrlin~ motor oil, brake-oil, L,~ ;on fluid, cooking oil,coffee, and wine.
Masonry and other porous surfaces may be made resistant to water and water-based liquids in one of two ways: by rendering the surface waterproof or by rendering the surface water repellent. A waterproofed surface is completely impervious to both liquid water and water vapor. A water repellent surface repels water but is sllb~ l1y permeable to water vapor. Mason Hayek, "Waterproofing and Water/Oil Repellency," 24 Kirk-Othmer Encyclopedia Of Ch~miç~l Technology 460-62 (3d ed. l9xx), for example, provides an overview ofthese effects.
Waterproofing of a surface is typically achieved by application of a "~en,l),~e such as vinyl chloride, polyvinyl chloride, polyethylene, or butyl rubber CA 02222139 1997-11-2~
W O 97/00230 PCT~US96/06313 or by application of a sea.ant such as tar, asphalt, paints, polyurethane, epoxy or mastics. While these waterproofing agents can offer excellent r~ci~t~nre to pen~ lion by water and water-based liquids, they often disadvantageously alter the appearance of the coated surface, ch~nging the color of the surface and leaving it S with a shine. Waterproofing l,~ ç~ also trap moisture within the treated surface, thereby promoting s In co~ sl, water repellents do not alter the app~r~lce of a porous masonly surface when applied as a Ll~ -l, and because a water repellent surface is permeable to water vapor, moisture does not become trapped in the masonry andspalling effects can be reduced. Water-repellent lle*l-"~ .c used commercially include metal stearates, oils, waxes, acrylates (both polymers and monomers), silicones (solvent-based and emulsion), siliconates, silanes and, more recently,fluororllPm~ s These compositions generally contain hydrophobic groups, such as a long-chain allyl group or polydilllelllylsiloxane, and functional groups, such as silyl or carboxyl, to bond either covalently or ionically to the masonry surface, which typically coll~aills high conce~ ions of silicon, calcium and ~lumimlm atoms. Tre~tm.ont~ made from these compositions are typically delivered from volatile organic solvents, which are undesirable because of the adverse environment~l and health effects associated with them.
Environmental conce- ~-s have spawned the development of a number of water-dispersed and water-çm--l~ified masonry L-~ . U.S. Pat. No. 4,648,904 (DePasquale et al.), for example, describes a shelf-stable aqueous emulsion useful to render a porous ceramic substrate water-repellent consisting essçnti~lly of a C 1 -C20 hydrocarbyl or halogenated hydrocarbyl silane and a nonionic emulsifying agent having a hydrophillic-lipophilic balance (~B) value from 4 to 15. Also, U.S. Pat.
No. 4,517,375 (Schmidt) discloses aqueous i.llpl~llation solutions prepared fromhydrolyzed alkyl trialkoxy silanes. While providing ecological advantages over solvent-based ~le.~ 7 these water-dispersed and water-~m--l~ified silane materials have not been evidenced to provide pclrollllance comparable to solventdelivered materials. Additionally, silane compositions do not provide si~nifir~nt protection from oil-based stains.

CA 02222139 1997-11-2~
W O 97/00230 PCTrUS96/06313 Only fluorochemical-co~ g ~ PI)IC offer si~nific~nt repellency to oil-based stains. U.S. Pat. No. 5,274,159 (Pellerite et al.), for example, describescertain water-soluble or dispersible fluorocarbylalkoxysilane surf~cf~nt~ which may be cured onto a masol ly surface. Additionally, Published World Patent Application S WO 9207886 describes an aqueous dispersion of a gelled particulate fluo,ole~"
that can form a protective film having good weatherability and good stain-resi~t~nce.

SUMMARY OF T~IE INVENTION
In one aspect, the present invention provides a water-soluble and shelf-stable aqueous fluorochemical polymeric trç~tmPnt useful to treat porous sub~ Les to render them repellent to water- and oil-based stains. The l,e~ .l comprises a water-soluble fluorochemical polymer co..~ g only carbon atoms in the backbone, with a plurality of each of the following groups pendent from the backbone: (a) fluoroaliphaticgroups, (b) carboxyl-co.~ groups, (c) oxyalkylene or polyoxyalkylene groups, and, optionally, (d) silyl groups. Typically, the llefl~ l polymers have interpoly",c;,i~ed units derived from one or more, and pr~ bly a plurality, of each of the following monomers:
(a) monomer selected from the group consisting of acrylate, meth~c.rylate, acrylamide, meth~crylamide, thioacrylate or meththioacrylate compounds co~-lAill;..g a fluoroaliphatic moiety that is linked to the residue of the compound through a divalent, organic linking group;
(b) monomer selected from the group consisting of acrylic acid, meth~-.rylic acid, carboxyalkylacrylate and carboxyalkylmeth~ylate compounds;
and (c) ",ono",er selectecl from the group cons,sli,lg of acrylate, meth~rylate, acrylamide, meth~crylamide, thioacrylate or meththioacrylate compounds COI~ g an oxyalkylene or polyoxyalkylene group linked to the residue of the compound through an oxygen, sulfur or nitrogen atom.

CA 02222139 1997-11-2~
W O 97/00230 PCT~US96/06313 Preferably, the polymer further inr.~ es interpolymerized units derived from mono,n~ selected from the group consis~ g of acrylate, meth~rylate, acrylamide, meth?~crylamide, thioacrylate and meththio~crylate compounds that contain a alkoxysilane moiety linked to the residue of the monomer through a divalent organic group. In another aspect, the present invention provides shelf-stable aqueous solutions or dispersions compli~ing the polymeric Lrç~ and a method of treating porous substrates to render them repellent to water- and oil-based stains using the arole"-t;"lioned polymeric product.
Because the water-soluble polymeric Ll e~ of the present invention, and the shelf-stable aqueous solutions thereof, can be applied to porous substrates in aqueous solution, they elimin~te the need for en~/i,ol.i~ lly harmful and toxic co-solvents. Particularly when applied to masonry and other siliceous materials, these polymeric L,~~ can react with the substrate onto which they are applied to form an invisible and water-insoluble coating that repels both water and oil, resists soiling, and that cannot be easily washed from the surface of the substrate.
Substrates treated with these polymers are thereby durably protected from rain and normal weathering.

DETAILE;D DESCRIPTION OF INVENTION
The water-soluble, fluorochemical polymeric tre~tm~nts useful in the invention col",u,ise compounds that comprise water-soluble fluoroçll~omic~l polymers co. ~I~;..il~g only carbon atoms in the backbone, with a plurality of each of the following groups pendent from the backbone: (a) fluoroaliphatic groups, (b) carboxyl-co..~ g groups, (c) oxyalkylene or polyoxyalkylene groups, and, 2~ optionally silyl groups.
Typically, useful lleaL",e,-L polymers comprise interpolymerized units derived from each of the following monomers:
(a) monomer selected from the group consisting of acrylate, methacrylate, acrylamide, meth~clylamide, thioacrylate or meththioacrylate compounds which contain a fluoroaliphatic moiety that is linked to the residue of the compound through an organic, divalent linking group;

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Siet:~rtstr 4 - 8~675 Munchen (b) monomer selected from the group consisting of acr~iic acid, methacrylic acid, carboxyalkylacrylate and carboxyalkylmethacr-.~te compounds;
and (c) monomer selected from the group consisting of acr.~ate, methacrylate, S acr~,lamide, methacrylamide, thioacrylate or meththicacrylate compounds that contain an oxyalkylene or polyoxvau~vlene group.
Other monomers may also be used to prepare the polymeric treatment, that do not interfere witll the water-solubility or the water and oil re~ellent properties of the product. Preferably the only monomer used in addition to monomers (a), (b) 10 and (c) to prepare the product is monomer selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, thioacrylate and meththioacrylate compounds and cont~ininv an alkoxysilane moiety linked to the residue of the monomer through a divalent organic ~roup. Preferably, a ?lurality of units derived from each of the aforementioned monomers are present in the polymer 15 and the units can be located randomly or in blocks or segments along the backbone of the polymer.
Preferably, the polymeric treatment ~,o~ l ises a polymer that can be represented by the following general formula:
( I
(-CR-CH2-)~(-CR-CH2-)b(-CR-CH2-)C(-cR-cH2-)d !
c=o c-~ c=o c=~
X (, ~ X

Rl C=O)m ROA R3 Rf O~ M+ Si(OR )i whel ehl:

AMENDED SI~EET

W O 97/00230 PCT~US96/06313 R is hydrogen or an aliphatic hydrocarbon group having from 1 to 4 carbon atoms;
Rfrep~~GsGIlls a fluoroaliphatic group having a perfluorinated carbon chain from about 3 to about 20 carbon atoms in length, more plerGl~bly having from about 6 to about 14 carbon atoms. Rf can contain straight chain, branched chain, or cyclic fluolh~dLed alkylene groups, or any such colllbinalion thereof. RfiSplGrGI~Lbly free of polymerizable olefinic unsaturation and can optionally contain caternary heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. A fully fluorinated radical is pr~,rGllGd, but hydrogen or chlorine atoms may be present as substituPntc provided that not more than one atom of either is present for every two carbon atoms. It is prGrGllGd that Rf contains about 40%
to about 80% fluorine by weight, more preferably about 50% to about 78% fluorine by weight The terminal portion of the Rf group is fully fluorinated, preferably co.. ~ g at least 7 fluorine atoms, e.g., CF3CF2CF2--, (CF3)2CF--,--CF2SFs or the like. Perfluorinated aliphatic groups (i.e., those of the formula CnF2n+l--) are the most pl'Gr~;llGd embodiments of Rf.
Rl represents an organic divalent connecting group having from 1 to 12 carbon atoms and is preferably ~yH2y--,--CON(Rs)CyH2y--,--So2N(R5)cyH2y--, or--CyH2ySO2N~Rs) CyH2y--, where Rs is hydrogen, methyl, ethyl, propyl, and butyl and y is independently selected from 1 to 6, preferably from 2 to 4;
X is indep~n-l~ntly selected as oxygen, nitrogen, or sulfur Preferably, X is oxygen or nitrogen;
R2 is a short chain alkylene group, such as methylene or ethylene;
m is either 0 or 1.
M+ is NH4+, NRnH4 n+, where R is an alkyl, aryl or alkylaryl group and where n may be between 0 and 4 inclusive, or M+ is an alkali metal CA 02222139 1997-11-2~

cation, or is a multivalent cation that does not adversely affect the water solubility of the polymer, such as Ca and Zn.
ROA is an oxyalkylene or a polyoxyalkylene group of the formula ~ -(C2H4O)p(C3H6O)q(C4HsO)rR6 where R6 is hydrogen or an alkyl or aryl group having from 1 to 4 carbon atoms and where p, q, or r can be zero, but their sum, p+q+r, must be a number greater than or equal to 1.
The maximum value of p+q+r will depend upon the value of c (the amount of oxyalkylene-co~ monom~r unit present in the polymer), and the value p+q+r and c are s~lecte~l such that the polyrneric product is water-soluble. Typically, p+q+r will be from about 2 to about 200. Plere- ~bly, ROA iS a hydroxypropyl group or COllLaillS a polyoxyethylene chain or a polyoxyalkylene chain conciefing of interpolymerized oxyethylene and oxypropylene units.
R3 l~;ples~llls an organic divalent connecting group having from 1 to 4 carbon atoms and is plere,~bly ~H2--, ~2H4--, ~3H6--or--C4H8--.
R4 is sloiected from the group col1si~l;llg of hydrogen, methyl, ethyl, propyl, and butyl.

The coefficients a, b, c, and d of Formula I represent the number of interpoly.l,~ ed monomer units for each mono~..er present in the polymer.
Rec~ ee the p~esence of the silyl-co~ g monomer in the polymer, though prt:rw,ed, is optional, the coefficient d as depicted in Formula I may be zero. The ratio of the conefitllçnt monomers in the polymer, reflected by the coefficients a, b, 25 c, and d, should be chosen to meet the following polymer requirements:
(1) a polymer number average molecular weight (Mn) of from about 3500 to about 30,000, plere-~bly from about 4500 to about 20,000;
(2) a molecular weight distribution, MW/Mn~ of greater than 1.5 preferably greater than 2;

CA 02222139 1997-11-2~
W O 97/00230 PCT~US96/06313 (3) from about 40% to about 80% by weight, plt;rt;l~bly from about 50% to about 70% by weight, of interpolymerized monomer units with pendent fluoroaliphatic groups;

(4) from about 5% to about 50% by weight, prerel~bly from about 5% to S about 25% by weight, of interpolymerized .llonol,ler units with pendent carboxyl functional groups;

(5) from about 5% to about 50% by weight, pre~l~bly from about 5% to about 35% by weight, of interpolylll~ ed l,lo,l~l.,er units with pendent oxyallylene-co"~ P functional groups; and (6) from 1 % to about 20% by weight, preferably from about 2% to about 15% by weight, of interpolymerized monomer units with pendent silyl-co..~ functional groups, if such monomer units are present.

RepleselllaLi~e fluoroaliphatic group-co~ g monomers useful for 15 making the polymers depicted by Formula I include the following:
C8F 1 7S02N(CH3)C2H40C(O)CH=CH2;
C8F 1 7S02N(C2H5)C2H40C(O)CH=CH2;
C8F 1 7so2N(c2Hs)c2H4oc(o)c(cH3)=cH2;
C8F I 7S02N(C4Hg)C2H40C(O)CH=CH2;
CgF 1 7cH2cH2oc(o)cH=cH2;
C7FlsCH2OC(O)CH=CH2; and the reaction product of one mole each of C8F17S02N(C2H5)C2H40H, Hoc3H6oc(o)c(cH3)=cH2 and toluene diisocyanate.
Repleselll~ e call ~,~yl group-co,~ ;"g Illono~,e~ useful for making the polymer depicted by Formula I include acrylic acid, meth~t~.rylic acid and ca,l,o~y~lhylacrylate.
Representative oxyalkylene group-co"l~i";,~g monomers useful for making the polymer depicted by Formula I include the following:
HOCH2CH2OC(O)CH=CH2, CA 02222139 1997-11-2~
W O 97/00230 PCT~US96/06313 HocH2cH2oc(o)c(cH3)=cH2 HOC3H60C(O)CH=CH2, and CH3 O(CH2CH20) 1 7C(O)CH=CH2, and ~ HO(C2H40)10(C3H60)22(C2H40)10C(O)CH=CH2~ each a poly~y~tl-ylene group-co.. l~;.. ;ng monomer.
RG,~rese..l~ e silyl group-cor.~ .;..g monomers useful for making the polymer depicted in Formula I include 3-acrylo~Lyl,rop~l L-i-l.Glllu~silane, 3-m~.th~r. yloxypropyl trimethoxysilane, and vinyl~ hc ~y~ilane.
The poly---eri~lion reaction to create the polymeric tre~tm~nt~ of this 10 invention may be carried out in a solvent (e.g., acetone, ethyl acetate, isopropyl alcohol, tetrahydrofuran or methylene chloride) or in a solvent blend in the presence of little or no water using from 0.5 to 2.0 weight percent of a ~L~dal d free radical polymerization initiator such as t-butylperoctoate (t-BPO) or 2,2'-azobisisobutyronitrile based on the weight of the monomers employed. Optionally,15 2 to 5 weight percent based on the weight of the monomers of a standard chaintransfer agent such as isooctylthioglycolate (IOTG) or p-G~,~bly a silane- or silanol-co..~ g chain l~nsrGI agent such as 3-mercaptopropylllilllGlhoxysilane (~TS) may also be used. The use of a chain transfer agent is not necesS~ry in a solvent such as THF which itselfprovides chain L~n~rGI properties, but is nece~s~ry 20 in a low free radical-co..l~;.,;..g solvent such as ethyl acetate to prevent the molecular weight from becoming excessively high and resulting polymers too viscous.
Af'ler the polylllGIi~lion is complete, the acidic copolymer solution or dispersion is neutralized with water co..~ g a base, prerel~bly ammonium 25 hydroxide, to form an emulsion. The solvent or solvents used in the reaction may then be stripped under vacuum to form a clear aqueous solution of the polymer without the need for external Pml-l~ifiers. During neutralization, any pendent silane groups, if present, hydrolyze to form free silanol groups. These groups will notself-crosslink to destabilize the ~queous polymer solution but will instead increase 30 the polymer's water solubility. Surprisingly, aqueous solutions ofthe reslllfin~
silanol group-co..l~ g polymers are in(l~finitely shelf stable at room tGIll~ re.

g CA 02222139 1997-11-2~
W O 97/00230 PCTrUS96/06313 The p,~sence of the silanol groups within the polymeric IIG~ I additionally allows the polymer to covalently react with a siliceous masonry surface, therebyimproving durability ofthe Lle~..e~.l Aqueous solutions of the polymers of the present invention may be applied 5 onto any porous substrate into which a liquid may imbibe, int l~ltlin~ masonry, textiles, carpets, pl~etics~ painted surfaces, and leathers, to render that substrate ;sL~L to soiling and repellent to water- and oil-based stains. Any method of application which produces a thin coating of the polymer on the substrate surface may be used, such as by spraying, p7/(~lling~ or pA;I~ P Once applied from 10 solution, the polymer tre~tmt~nte may be dried onto the substrate either under ambient conditions or at elevated temperatures to produce a long-lasting repellent surface that does not change the appe~nce of the masonry. Application of a smallamount of a multivalent hydroxide, e.g. calcium hydroxide, may also be added to a dilute aqueous solutions of the polymer prior to application of the L~ to a15 polished surface to f~cilit~te the removal of excess coating from the surface. As a result ofthe penetration ofthe polymer L~l.n~..le into the porous substrate surface, these tre~tmt~nts generally additionally prevent adsorption of st~ining fluids into the substrate (i.e., fluids will not soak in), even after extensive outdoorexposure, since the coating below the surface is not degraded.
The following examples are offered to aid in a better undc;l ~ tl;,-g of the present invention and are not to be u.-l-eces~.ily construed as limiting the scope thereof.

EXAMPLES
Test Methods The test methods used to evaluate the p~lro""ance described in Examples and Col"~,a,~Li~e Examples infra are described below.

30 Cement Tile Ple,oa,~Lion, Tl~ t~ Application CA 02222139 1997-11-2~

Cement tiles of 30 cm length by 10 cm width by 1 cm thickness were pl~l)a ed from concrete (or mortar) according to the procedure described in ASTMC 109-92, Section 10, but without tamping. The wet cement surface of each tile was given a broom finish prior to curing. Each tile was allowed to cure for at least 5 two weeks at ambient conditions prior to testing. For testing, each cured tile was divided into either 7 sections (each 4 cm by 9 cm) or 9 sections (each 3 cm by 9cm) with a dividing product (Plastic Dip~M coating~ made by PDI Inc., Circle Pines, MN). The desired ~ was applied and spread evenly with an ~yedroppel one time to only one side of a cured tile section at a spreading rate of 160 square feet per gallon, or 40 cm2/g (0.92 g for a 4 cm by 9 cm section or 0.67 g for a 3 cm by 9 cm section). Each treated tile was allowed to dry for at least 12 hours under ambient laboratory conditions.

Scrubbing Test to Measure Durability To determine the ~ ll.e.. l's durability, the following scrubbing test was used. A detergent solution was prepared consisting of 60 g DawnTM liquid dishwashing soap mixed with 940 g tap water. Each treated cement tile had its dividing product removed and was mentally divided into lengthwise halves: one half was left as is, and the other half was scrubbed. The scrubbed half was first 20 cont~cte~l with water, then with about 2 mL of detergent solution. The wet surface was scrubbed back and forth three times with a 12 cm by 3 cm stiff nylon bristlebrush held lengthwise, then was rinsed with water. The scrubbing and rinsing procedures on the half were repeated two more times, and the tile was allowed todry under ambient conditions.
Water Absorption Test (WAT) A Rilem tube was used to measure the rPci~t~nce of a treated cement tile to penetration by a hydrostatic head of water (the pressure on the tile is directlyproportional to the height of water in a Rilem tube). This test was adapted from30 Rilem (Co-------ssion - 2.5 Test Method II.4).

CA 02222139 1997-11-2~
W O 97/00230 PCT~US96/06313 A Rilem tube, having a height of 7 inches (18 cm), a base ~ metçr of 2.5 cm and an upper section with a ~ elçl of 1 cm and a gradu~ted volume scale of 10 mL, was ~tt~chçd to either the scrubbed or the unscrubbed tile halfusing 3M
Press-In-PlaceTM Caulk. The tube was filled with s--ffi~ient water to bring the water level 8.0 cm above the substrate surface and a water volume reading was taken.
A~er 20 mim~tçc, a new water volume reading was taken and the number of millilitçrs of water absorbed by the treated tile was c~lcul~te~i by subtracting the two re~ling~ The Water Absorption Value reported is ten times the number of millilitçrs of water absoll,ed (e.g., if 0.5 mL of water were absorbed, the Water Absorption Value would be 5).

~pot Test A Spot Test was used to visually rate the ability of the treated cement tile to prevent a test fluid drop from st~ining the cement after a given exposure period, both before and after scrubbing.
Scrubbed and unscrubbed treated sectioned cement tiles were challenged with 0.1 mL drops of the following stains:
DOT 3 motor vehicle brake fluid (conroln's to Fed. Standard 116; Fed. Specification U-V-6801 & SAE J1703) with added FDC Color Blue #1 dye (BFL) Paul MassonTM burgundy wine (WIN) Hot bacon grease; Corn King~ Bacon, cooked, grease recovered, preheated to 110~C (HBG) PennzoilTM ATF Automatic tr~n~mi~it)n fluid (ATF) HokanTM sesame seed oil (SSO) Water saturated with Taster's ChoiceTM coffee (COF) Used 10W30 motor oil (taken from a 1980 Buick Skylark, 5,000 mi.) (UMO) A~er 16 hours, the drops were removed by using the aro,t;l,.enLioned scrubbing and rinsing procedure.

CA 02222139 1997-11-2~
W O 97/00230 PCT~US96/06313 The following S-point scale was used to rate the Spot Test pelr,.~ ce of the lle~ ll on the scrubbed and unscrubbed tile surfaces, 0 lcples~ g the best rating:
0 = no visible stain 1 = traceofstainvisible 2 = outline of drop barely visible 3 = outline of drop visible 4 = dark outline of drop 5 = dark stain which has spread Total Rating The Total Rating is the sum of the Water Absorption rating and Spot Test ratings and repl t;stllls an overall repellency rating for that particular l, e~ when applied to a concrete tile.
Weather-O-Meter Test One set of treated cement tiles was given an accelerated weathering test as described in test procedure ASTM G-26, with a Type B exposure ap~a.~ s. The testing equipment was a water-cooled AtlasTM ARC, Model 65XW~ or CI 65 20 (available from Atlas Electric Devices Co.), co..l~ g a 6500 watt xenon light source with borosilicate inner and outer filters, giving an irradiance of 0.35 w/m2.
Test samples were exposed for 168 hours to repeating cycles of 102 mimltes of light at black-panel temperature 63 +/- 3 ~C followed by 18 minlltes of light with water spray at te~ )e-~L~Ire 16 +/- 5 ~C.
Plepalalions Of Polymers Evaluated A list of ac,~,,yllls for the monomers, initiators and chain-L,~1srel agents used to make the polymers evaluated as masonry ll eall.lenls is presented in Table 1.

Table 1 Monomer Full Name or Structure MeFOSEA CgF17SO2N(CH3)C2H4OC(O)CH=CH2 (can be made by reacting C8F17SO2F, available from 3M Co. as FluoradTM Fluoroch~mic~l Intermetli~te FX-8, with N-methyl-2-~minoeth~nol to form CgF17S02N(CH3)C2H40H, which is further reacted with acryloyl chloride) EtFOSEA CgF 17SO2N(C2H5)C2H4OC(O)CH=CH2 (available from 3M as FluoradTM Fluorochemical Acrylate FX-13) TelomerA C~F17C2H4OC(O)CH=CH2 (made by reacting ZonylTM
BA, fluorochemical alcohol, available from DuPont, with acryloyl chloride) A-174 3-meth~cryloxypropyl trimethoxysilane (available from Union Carbide) AA acrylic acid CEA J3-carboxyethyl acrylate CW450A CH3O(CH2CH2O)loc(o)cH=cH2 (made by reacting CarbowaxTM 450, a 450 molecular weight monofunctional polyethylene oxide available from Union Carbide, with acryloyl chloride) CW750A CH3O(CH2CH2O)17C(O)CH=CH2 (made by reacting CarbowaxT~ 750, a 750 molecular weight monofunctional polyethylene oxide available from Union Carbide, with acryloyl chloride) BA n-butyl acrylate IOA isooctyl acrylate HPA 13-hydlo~y,ulopyl acrylate hi~tor Full Name or Structure AIBN 2,2'-azobisisobutyronitrile (available from DuPont as VazoTM 64 initiator) TBPO t-butyl peroctoate (available from Atochem North America, Inc.) Chain Trans. Agent Full Name or Structure IOTG isooctylthioglycolate (availablefrom~A~ s~ e Chemical Corp, L~"~in~,lon, Mass.) MPTS 3-~ c~lop~l)pylLl;lllt;lhoxysilane (availablefromHuls America, Inc.) Ple~ ion of Polymer Pl A 4-ounce (113 g) narrow-mouth bottle was charged with 13 g of MeFOSEA, 1 g of A-174, 2 g of AA, 4 g of CW750A, 0.4 g (2%) of TBPO
5 il,iLalor, and 30 g of tetrahydrofuran (THF) to make a polymer with a theoretical monomer weight ratio of 65/5/10/20 MeFOSEA/A- 174/AA/CW750A. The bottle was purged with nitrogen for applo~i"laLely 5 mimlte~, was sealed, and then was heated with agitation in a water bath at 65~C for 4-5 hours, After that time, 30 g of the res~-ltin~ polymer solution was mixed with 50 g of water and 2 g of 28%
10 aqueous NH4OH. The neutralized polyrner solution was distilled at a pressure of approxi,l,ately 300 mm Hg, with THF coming offat 30-35~C, initiator by-product and water coming offat 35-60~C, and water coming offat 60~C. Di~till~tion contin-~ed until only water was coming offand the neutralized polymer solids in the g water had formed a fluid, relatively clear aqueous concel,l, aLe of between 20 and 40% solids by weight. This concentrate was diluted to 3% (wt) solids withwater to form a clear aqueous premix solution to be used for the masonry l,~~
tests.

CA 02222139 1997-11-2~

epal ~ion of Polymers P2-P9 Polymers P2-P9 were made in THF in the same way as was Polymer P 1 in Example 1 except that the charges of MeFOSEA, A-174, AA and CW750A were varied as shown in Table 2.

Table 2 Polymer MeFOSEA/A-174/AA/CW750 Charges (~rams) (theo. wt % of polymer) P2 12.4/1.0/1.0/5.6 62/5/5/28 P3 13.0/1.0/3.0/3.0 65/5/15/15 P4 13.0/1.0/4.0/2.0 65/5/20/10 PS 13.0/1.0/2.0/3.0 70/5/10/15 P6 13.0/2.0/1.5/3.5 65/10/7.5/17.5 P7 13.0/3.0/1.5/3.5 60/15/7.5/17.5 P8 11.0/4.0/1.5/3.5 55/20/7.5/17.5 P9 13.6/0.0/2.0/4.4 68/0.0/10/22 For Polymers P2-P9, 20-40% aqueous conce"l,~les and 3% aqueous premix solutions were all fluid and relatively clear, represçl-l;"g monomer weight percçnt~s ranges of 55% to 70% for MeFOSEA, 0% to 20% for A-174, 5% to 20% for AA, and 10% to 28% for CW750A.

Pl epa, ~Lion of Co-l")a, ~ e Polymer CP 1 Col"pa, ~ e Polymer CP 1 was made in the same way as was Polymer P 1 in Example 1 except that the charge of MeFOSEA was 13.0 g, A-174 was 1.0 g, AA
was 6.0 g and CW750A was omitted, giving a polymer with a theoretical monomer weight ratio of 65/5/30 MeFOSEA/A-174/AA. This polymer gelled during the polymerization at 65~C, making it useless as a masonry tre~tm~nt, thus showing the adverse effect of omitting the oxyalkylene group-co~ ;";l-g monomer from the 20 polymer.

P-tpa,~lion of Col..pa-~Li~e Polymer CP2 Colnpa~ e Polymer CP2 was made in the same way as was Polymer P 1 in except that the charge of MeFOSEA was 13.0 g, A-174 was 1.0 g, CW750A was 6.0 g and AA was omitted, giving a polymer with a theoretical monomer weight 5 ratio of 65/5/30 MeFOSEA/A-1 74/CW750A. Though the resl-lting polymer ~ formed a fluid solution in tetrahydrofuran during the poly.. e.i~lion at 65~C, the aqueous solution did not clear up upon removal by ~lietiil~tion ofthe T~, initiator by-product, and some water. When the con~ntrated was diluted to 3% (wt) solids with water, a p-e~ le formed, which is undesirable for a shelf-stable masonry 10 ~ ..l These results show the adverse effect of o.. ~ g the carboxyl group- co..~ g monomer from the fluorochemical polymer ofthis ~x~ plc.

:E~xamples 1-9 In Examples 1-9, Polymers Pl-Pl9 were applied as 3% (wt) solids aqueous 15 premix solutions to cement tiles to deterrnine the effect of varying the conce,lll~Lion of fluoroaliphatic group-co.,l~ monomer, carboxyl group-co.~ -g monomer, polyoxyalkylene group-co..l~ g mono~ and silyl group-co..l~;..il-~ monomer in the polymer. Results from these treated cement tile tests are presented in Table 3.
For the water penetration and stain resistance test data, the number presented 20 before the slash was measured on unscrubbed treated tile, while the number presented a~er the slash was measured on scrubbed treated tile.

Co..lpal~ e Example Cl In Col-.pa-~ e Example C 1, a commercially used fluorochemical-based 25 repellent emulsion, Scotchgard TM FC-364 Carpet Protector, was diluted to 3%
(wt) solids with water and was applied to a section of a cement tile and evaluated as described in Examples 1 1-20. Table 3 p- t;~.-ls the results.

CA 02222139 1997-11-2~
WO 97/00230 PCT~US96/06313 Table 3 Results of Water and Stain Tests E~ Polg~er WAT BFL WrN HBG ATF UMO SSO COF TOTAL
Pl 0/1 1/2 3/3 1/3 1/3 2/4 1/3 3/3 12/22 2 P2 1/1 3/3 2t3 0/3 0/3 0/4 0/4 3/3 9/24 ClFC-364 4/4 4/4 3/3 4/4 3/5 3/3 2/4 3/4 26/31 The data of Table 3 show that the polymers of this invention all oulp~lro~ ed the FC-364 as a durable water and oil resistant masonry repellent.
5 Polymer P9, co..~ .;llg no pendent silyl groups, performed colllp~bly to Polymers P l-P8, which do contain pendent silyl groups, in-iicAting that the presence of pendent silyl groups in the polymer is not required to attain a durable lIeA
resistant to water pene~ ion and to st~ining 10 Pl e~ lion of Polymers P 1 0-P 15 Polymers P10-P15 were made in THF using the same monomers, the same theoretical monomer ratios and the same bottle polymerization procedure as described to make Polymer P 1 but the molecular weights of the polymers were varied by incorporating various levels of initiator and chain-~ agent. Number 15 average molecular weights (Mn) and weight average molecular weights (Mw) of the polymers were determined by gel permeation clllu~ lography using a polystyrene standard. The acidic polymers were then neutralized in aqueous NH40H using the same procedure as with Polymer Pl and the T~ was stripped away, giving aqueous concellll~les co..~ g the neutralized polymer at 40-50 (wt) % solids.

W O 97/00230 PCTrUS96/06313 These concentrates were then diluted to 3% (wt) solids with water to form aqueous premix solutions to be used for the masonry tre~tment tests.

P~ lion of Polymer P 10 S Polymer P10 was p- "~)aled by charging 13 g MeFOSEA, 1 g MPTS (using 5% 3~ .c~loll;...~ y~ilane as both si1ane con~tit~l~nt and chain-ll~.~rel agent), 2 g AA and 4 g CW750A. The number average mole~ r weight of the polymer was dt;l~;;ll.lined to be 3500, with an MW/Mn ratio of 1.574.
The aqueous conce~ le reSlllting from the neutralization and THF strip steps was fluid and nearly clear. Diluting the concentrate to 3% (wt) solids with water formed a clear aqueous premix solution initially ~ee of any ple~ipilale, and after 48 hours formed a slight pl ecipilate.

Pl ~>al ~Lion of Polymer P 11 Polymer Pl l was p-e~aled by charging 13 g MeFOSEA, 1 g A-174, 2 g AA, 4 g CW750A and 0.4 g (2%) MPTS. The number average molecular weight of the polymer was deterrnined to be 5460, with an MW/Mn ratio of 2.134.
The aqueo~s conce-~ le rç~ltin.~ from the neutralization and THF strip steps was fluid and nearly clear. Diluting the COllCellll ~Le to 3% (wt) solids with water formed a clear aqueous premix solution initially free of any p- t;dpil~le, and after 48 hours formed a slight pl ecipilale.

P~e,o&l~lion of Polymer P12 Polymer P12 was prepared by chalgi-lg 13 g MeFOSEA, 1 g A-174, 2 g AA, 4 g CW750A and 0.1 g (0.5%) TBPO initiator. The number average molecular weight of the polymer was determined to be 6300, with an MWlMn ratio of 4.72.
The aqueous concentrate res~llting from the neutralization and THF strip steps was fluid and nearly clear. Diluting the concentrate to 3% (wt) solids with water forrned a dear aqueous premix solution free of any ~cd~ilale.

CA 02222139 1997-11-2~

P, epal ~lion of Polymer P 13 Polymer P13 was prepared using the same procedure as with Polymer P12 5 except that 0.2 g (1%) TBPO initiator was used. The number average molecular weight of the polymer was dete-,llined to be 7560, with an MW/Mn ratio of 4.39.
The aqueous concentrate re.s..l~ing from the neutralization and THF strip steps was fluid and nearly clear. Diluting the collcellllale to 3% (wt) solids with water formed a clear aqueous premix solution free of any pl eci~ilale.
Prel)a- alion of Polymer P 14 Polymer P14 was p~epaled using the same procedure as with Polymer P12 except that 0.4 g (2%) TBPO initiator was used. The number average molecular weight of this polymer was determined to be 7771, with an MW/Mn ratio of 5.11.
The aqueous concentrate r~c -lting from the neutralization and THF strip steps was fluid and nearly clear. Diluting the concentrate to 3% (wt) solids with water formed a clear aqueous premix solution free of any pre~;ipilate.

~1 e~)a. ~Lion of Polyrner P 15 Polymer Pl S was prepared using the same procedure as with Polymer P 12 except that 0.4 g (2%) TBPO initiator was used and 0.4 g (2%) of IOTG chain-Il ansrer agent was added. The number average molecular weight of this polymer was d~l~;llllined to be 5500, with an MW/Mn ratio of 2.2.
The aqueous concentrate re~C~lting from the neutralization and THF strip steps was fluid and nearly clear. Diluting the conctllll~te to 3% (wt) solids with water formed a clear aqueous premix solution free of any p~ e~ uilale.

Ex~mples 10-15 In Examples 10-15, Polymers P10-P15 were applied as 3% (wt) solids aqueous premix solutions to cement tiles to determine the effect on water and stain reeict~nce of varying the molecular weight of the polymer. Results from these CA 02222139 1997-11-2~
W O 97/00230 PCT~US96/06313 treated cement tile tests are presented in Table 4. Again, as in Table 3, the number presented before the slash was measured on unscrubbed treated tile, while the number presented after the slash was measured on scrubbed treated tile.

Table 4 Results of Water ~nd Stain Tests E~ 1~ ~Mol. Wt. WAT BFL WINHBG ATFUMO SSO COF TOTAL

11 P11~460 0/2 0/1 1/30/2 0/20/3 0/2 2/2 3/17 Results from Table 4 show that good re~i~t~n~e to water penell~Lion and s~ p was ~ ed with all polymer molecular weights, with somewhat ~liminieh~ p~,r~llllance noted at the lowest molecular weight of 3~00.
Plepal~lion of Polymers P16-P18 Polymers P16-P18 were made in the same way as Polymer Pl except: in Polymer P16, TelomerA was substituted for MeFOSEA; and in Polymers P17-P18, CW450A and HPA respectively were substituted for CW750A. The reslllting 15 aqueous concentrate and 3% premix solutions were all fluid, relatively clear and free of any pl e-,ipilale.

Examples 16-18 In Examples 16-18, Polymers P16-P18 were applied as 3% (wt) solids 20 premix solutions to cement tiles and were evaluated for water penetration and stain ~, resict~nce. Results from these tests are presented in Table 5.
/

CA 02222l39 l997-ll-2~

Table 5 Results of Water and Stain Tests E~ Polymer WAT BFL W~N ~BG ATF UM O SSO COF TOT ~

The data in Table 5 show that CW750A, CW450A and ~A
polyoxyalkylene monomers all contribute co,l")a,~ble water barrier and stain re~iet~nce pe,rolll,ance, indicating that ~ignific~nt variation in nature and molecular weight of oxyalkylene monomer is possible within the scope of this invention.
Somewhat ~l;...;nicl~ed pe,r."l"al1ce was observed when TelomerA was substituted10 for MeFOSEA.

P,cpa,~lion of Co",l)a,~live Polymer CP3 Cor,,p~Live Polymer CP3 was made in the same way as was Polymer P1 except that MeFOSEA was charged at 13.0 g A-174 at 1.0 g, AA at 2.0 g and BA
15 a hydrophobic monomer, at 4.0 g. When the last portion of THF was stripped from this neutralized polymer aqueous solution, the solution became cloudier as colll,ualed to when the aqueous solution of Polymer P 1 was stripped of THF in which case the aqueous solution stayed nearly clear during the entire THF ~l,ipping process.
Plcpa,~lion of Conlp~live Polymer CP4 Co",p~live Polymer CP4 was made in the same way as was Polymer P1 except that MeFOSEA was cha~ged at 2.2 g, A-174 at 4.4 g, AA at 2.2 g and IOA, another hydrophobic monomer, at 4.0 g. When the last portion of THF was 25 stripped from this neutralized polymer aqueous solution, the solution again became W O 97/00230 PCTrUS96/06313 cloudier as colllpared to when the aqueous solution of Polymer Pl was stripped of THF.

Co~ )a,~ e E~a"~plcs C2-C4 In Co-~ e F~ IeS C2-C3, Co~--pal~ e Polymers CP3 and CP4 J were diluted with water to a level of 3% (wt) solids content, were applied to cement tiles as in Example 1, and half of each treated tile was evaluated for water penel-~lion and stain ,eei~ ce~ Then the treated tiles were subject to the earlier desc.il,ed Weather-O-Meter weathering test and were r~me~cll~ed for water pe le~ ion and stain l e~ ce7 as presented in Table 6 The numbers tabulated before the slash show measulel..e..ls done before weathering, while the numbers hblll~ted after the slash show measurements after weathering In Cc,---pa- ~ e Example C4, the same procedure was used as with Co---p~ e E~ ,les C2 and C3 except that DowTM 777 Water Repellent, a conll--el cially available waterproofing agent conslsling essç~ ly of potassium methyl siliconate, was used instead of Col,lpal~ e Polymer CP3 or CP4 Results are prese"led in Table 6 Examples 19-20 In Examples 19-20, the same procedure was followed as in Coml)alali~re Examples C2 and C3 except that Polymer P 1 and Polymer P18 were used respectively instead ofthe cGlllpal~ e polymers Results are presented in Table 6 CA 02222139 1997-11-2~

Table6 Test Results Before and After W~ g Ex. Pol. WAT BFL WIN ~IBG ATF UMO SSO COF TOT.

The data in Table 6 show that Polymers P1 and P18, polymers of this invention, demonstrate better water penetration and stain rÇcict~n~e than the co~ Li~e but related L~ e~ C, both before and after we~Lh~ lg. It is particularly sUl~Jlisillg that Polyrners P1 and P18, co~ g more hydrophilic monomer-derived content, would concictçntly ollLpelrollll Colllpa~ e Polymers CP3 and CP4, which contain more hydrophobic monomer-derived content.

F.xamples 21-25 As .cim~ tion tests to predict product long-term shelf life, 22% (wt) concentrate and 3% (wt) premix aqueous Polyrner Pl solutions were submitted to oven aging and freeze-thaw cycle tests. The oven aging test consisted of placingsamples of aqueous polymer solutions in a forced air oven adjusted to 60~C for aperiod of 10 days, then removing the samples and allowing them to cool to ambient lab temperature. The freeze/thaw cycle test consisted of 10 cycles of freezing aqueous polymer solutions at -20~C followed by thawing at 70~C. In Example 21, reCict~nce to water penetration and st~ining was measured by treating cement tiles with 3% premix freshly plepared (i.e., before oven aging or freeze-thaw cycling tests) by diluting a 22% concentrate. In Examples 22 and 23, 3% premix solutionswere plepal ed as in Example 21, except that the premix solution was oven aged or run through the freeze-thaw cycle test respecLively prior to testing for resistance to water penetration and st~ining In Examples 24 and 25, the 22% concentrate was oven aged or run through the freeze-thaw cycle test respectively prior to testing for CA 02222l39 l997-ll-2S
WO 97/00230 PCT~US96/06313 resi~t~n-.e to water ~ lion and ~ then was diluted to a 3% solution for testing. In all cases, numbers before the slash represe"l initial water penetration or g measu- c~ s, while numbers presented after the slash l~)l~se.ll measurements done after scrubbing as previously described. All the test results for 5 Examples 21-25 are presented in Table 7.
., .
Table 7 Te~ t Resu ts Befo ~e And After Scrubb ng E~. o/Orl Aging WAT Bli~ WIN HBG ATF UMO SSO COF TOT.
Test 21 3 None 0/0 0/2 1/3 0/2 1/2 1/3 0/3 1/1 4/16 22 3 Oven 1/0 0/1 1/3 0/2 0/2 2/3 0/2 1/1 5/14 23 3 Frz./Thaw 1/1 0/1 1/3 1/3 1/2 2/3 1/2 2/2 9/17 24 22 Oven 1/0 1/1 2/3 2/3 1/2 2/3 1/2 2/2 12/16 25 22 Frz./Thaw 0/0 1/1 2/3 2/3 2/2 2/3 1/2 1/1 11/15 T~,e d$ia in Table 7 show tnat the aged 22% concentrate and aged 3%
aqueous premix solutions of Polymer Pl were only slightly worse than the unaged solution in initial resi~t~nse to water penetration and st~inin~ and showed ee~nti~lly no di~re-Gnce in pe,ro~."allce after one scrubbing. All solutions showed minim~lclo~1~in~s or seciiment after aging, which was surprising in that the silyl groups of Polymer P 1 would normally be expected to crosslink or degrade under these severe aging conditions, especially during the oven aging tests.

Example 26 The same set of aging experiments was run as in Examples 21-25 except that Polymer Pl was substituted with Polymer Pl9, a polymer of this invention col~lAi,.i.~g no pendent silyl groups. Polymer Pl9 was theoretically a 64/18/18 (wt) terpolymer of MeFOSEA/AA/CW750A, made using the same procedure as used to make Polymer 1 except that MeFOSEA was charged at 12.8 g, AA at 3.6 g and CW750A at 3.6 g. Polymer P19 (cc,..l~;nil-g no pendent silyl groups) gave çssçnti~lly the same resistance to water penel, ~ion and st~ining as Polymer P 1 CA 02222139 1997-11-2~
W O 97/00230 PCTrUS96/06313 (c~ i..g pendent silyl groups) before and after oven aging and before and after one scrubbing.

Example 27 and Co"")a~ te Examples C5-C9 S The r~ei~n~e of masonry lleAI~ to particulate soiling was determined using the standard tile prepalaLion test previously described. Cement tiles weretreated with the polymer solution of each eAa~ lc. After each coating had dried and cured, a synthetic oily soil mixture coh~ g of 8% (wt) carbon black dispersed in mineral oil was applied, spread around, and ground into the treated slab 10 surface. After 10 min~ltes~ the panel was scrubbed with an aqueous solution of DawnTM Dishsoap Solution using a nylon bristle scrub brush. After scrubbing, thetreated surface was rated for soiling using a six point scale, where 0 ~ senls no soiling visible after scrubbing, S repl ese"ls no removal of soil after scrubbing, and 1, 2, 3 or 4 re,o~s~ g interme~ te levels of soiling re...~;..;..g In Example 27, the mortar slab was treated with a 3% premix solution of Polymer P18 prior to soiling. After scrubbing, the treated slab was given a rating of 1, inrlic~ting that only a small portion of the oily soil mixture r~m~ined In Con,pal~ e Example C5, the mortar slab was treated with HMKTM
Silicone Impregnator S34, available from HMK Germany, a division of Europe East-West Trading Company, prior to soiling. After scrubbing, the treated slab was given a rating of 5, indicating that virtually none of the oily soil mixture had been removed.
In Cc,lllpalali~e Example C6, the mortar slab was treated with Thompson's Water SealTM Protector (believed to be a solution of ~lllminl ~m stearate in mineral spirits) prior to soiling. After scrubbing, the treated slab was given a rating of 5, in~iic~tin~ that virtually none of the oily soil mixture had been removed.
In Colllpal ~ e Example C7, the mortar slab was treated with DowTM 777 Water Repellent prior to soiling. After scrubbing, the treated slab was given a rating of 5, in~ tinp that virtually none of the oily soil ~ Lule had been removed.
In Conlp~ e Example C8, the mortar slab was treated with n-octyl triethoxysilane (no water, ess~nti~lly a 100% solids reactive liquid) prior to soiling.

= CA 02222139 1997-11-25 After sc, ubbing, the treated slab was given a rating of 5, indicating that virtually none of the oily soil mixture had been removed.
In Co~ Li~te Example C9, the mortar slab was treated with 3% (wt active) of ScotchgardTM FC-3537 Fabric Protector in n-octyll,iell,oxy~ilane prior to S soiling. After scrubbing, the treated slab was given a rating of 4, indicating that v only a small portion of the oily soil mixture had been removed. Thus, even h~co~l~o~ling a good con.",ercially used oil-repellent fabric ~ A~ I into a goodcol.""Grcially used water-repellent silane did not improve the silane's rto~ .nee to soiling.
E~a",?les 28-41 and Co",pa,ali~e Examples C10-C23 In Fx~ r,lçs 28-40, various masonry substrates were treated with a 3%
(wt) ~qqueQus solution of Polymer Pl 8 at various application d~o.n~iti~s were allowed to dry and cure, then were subjected to the standard water penetration and st~ining 15 tests along with the particulate soiling test used in Fx~mple 27 (under he~riing of "SOIL") and to a stain test using PrestoneTM a"lir,ee~e (under he~-ling of "AFZ") In Con,p~ e Examples C10-C22, the same water penc;l,~lion and st~inin~ tests were run on the ullllealed masonry substrates. In Example 41, Pol,vmer Pl 8 was evaluated to treat southern white pine (to sim~ tc, for inst~ncp~ treating an outdoor 20 wooden deck), while in Conlpa, ~ e Example C23, no l, e~ was used on the pine. Results of these tests are presented in Table 8. The entry "N" means that the test was not run.

Table 8 E2~.Used (ft2/gal) SOIL En3G WIN ATF UMO SSO COF AFZ
28 White Thassos Marble 500 N 0 0 0 N 0 0 N
29 Quany Tile 500 N 0 0 0 0 0 0 N
Gypsum Drywall 150 1 0 2 0 0 0 N N
31 ~;~nrlct~n~o 150 1 2 1 1 0 0 N N
32 Sierra White Granite 500 1 1 0 1 1 1 1 N
33 rol~làin Tile, Textured 500 0 0 0 0 0 0 0 N
34 Honed T.- - 500 N 0 0 N N 0 0 N
Slate 500 N 0 0 0 0 0 0 N
36 Red Brick, Rough 150 2 N N N N N N N
Tex~ured 37 Terra Cotta 500 1 0 1 0 0 0 0 N
38 C~rnPli Flamed Granite 500 2 0 0 0 0 0 0 N
39 Red Brick, Smooth Face 500 N 0 N 0 0 0 N N
Asphalt, Parking Lot 150 N N N 0 0 0 N
41 Southern Pine 500 1 0 0 N 0 1 0 N
C10 White Thassos Marble ___ N 1 3 2 N 1 3 N
Cl 1 Quarry Tile ___ N 4 2 4 4 2 2 N
C12 Gypsum Dlywall ___ 4 4 4 5 4 5 N N
C13 .S~ ct~n~o 1 5 4 3 N N
C14 Sierra White Granite ___ 5 5 2 5 5 5 2 N
C15 ru-~la;l. Tile, Textured ___ 3 o o o o o o N
C16 Honed Lim~st~nlo ___ N 5 3 N N S S N
C17 Slate __ N 5 4 S S S 0 N
C18 Red Brick, Rough ___ 4 N N N N N N N
Textured Cl9 Terra Cotta ___ 4 5 1 5 5 5 5 N
C20 r~rn~ Flamed Granite ___ 4 5 5 5 5 1 ~ N
C21 Red Brick, Smooth Face ___ N 4 N 4 4 4 N N
C22 Asphalt, Parking Lot ___ N N N 5 5 5 N 5 C23 S ' Pine ___ 4 4 3 N 5 4 5 N

CA 02222l39 l997-ll-25 The data in Table 8 show that màsonry l~ s of this invention are useful for protecting a wide variety of masonry surfaces and are also usefill for protection of wood.
s J Example 42 and Colllpalali~e Examples C24-C27 In Example 42 and Co,-,p~ e F~mrt~ C24-C27, Polyrner 1 and a wide variety of water-based polymeric fluoroch~mic~l repçll~nt emulsions were appliedas 3 wt% aqueous solutions to cement tiles, were allowed to dry and cure, and then were evaluated for re~i~t~nee to water penellalion and st~ining Scolchga~dTM
Fabric Protectors FC-248 and FX-1860 are hydrophilic polymers desi~ned for release of stains and soils during laundering from soiled te7~tiles. Scolcl1ga,~Fabric Protector FX-327 Fabric Pl ole.;Lor is a hydrophobic oil and water repçlkor~t for textiles showing excellent long-term repellency. Collll,alali~e Polymer CP3 is a polyrner identical in composition to Polymer P 1 except that it co~ s n-butyl acrylate instead of hydrophilic polyoxyethylene acrylate. As before, tests were run before and a~er scrubbing and the corresponding results are presented before andafter the slash respectively in Table 9.

Table 9 Test Results Before and After Weathering Ex. Pol. WAT BFL W~ ~BG ATF UMO SSO COF TOT.

The data of Table 9 show that Polymer P1 o~lL~ rolms FC-248, FX-1860 and Colllpala~ e Polymer CP3. While P1 shows colllp~able pelrollllallce to FX-327, unlike FX-327, the aqueous solution of P1 is solvent-free.

CA 02222139 1997-11-2~
W O 97/00230 PCT~US96106313 Examples 43 and 44 For Examples 43 and 44, two pieces of cotton fabric 17.8 cm by 11.4 cm were completely i..lllle.~ed in a 3 wt% aqueous solution of Polymer 18. The fabric of Example 43 was dried for 48 hours in an oven held at 105 ~C . The fabric of 5 Example 44 was left to dry for 48 hours at room teln~ re.
The treated samples were evaluated for oil repellency using 3M Oil Repellency Test III (February 1994), available from 3M Company, Saint Paul, Millneso~a. For the test, the treated samples were çh~llP.nged to penetration by oils or oil mixtures of varying surface ten~ioni Oil and oil n~ uleS are given a 10 standard rating collespol1ding to the following.

Oil Repellency Rating Number Oil Composition mineral oil 1.5 85/15 (vol.) mineral oiVn-hex~dec~ne 2 65/35 (vol.) mineral oiVn-heY~iec~ne 3 n-h.oY~dec~ne 4 n-tetr~dec~ne n-dodecane 6 n-decane In running the test, a treated sample is placed on a flat, hol izc,lllal surfaceand five small drops of an oil or oil mixture are gently placed at points at least two inches apart on the surface of the sample. If, after observing for 10 seconds at a 25 45~ angle, four ofthe five drops are visible as sphere or a hell.i~hele, the sample is deemed to pass the test for that oil or oil mixture. The reported oil repellencyrating co..esponds to the most penetratirlg oil (i.e. the highest numbered oil in the above table) for which the treated sample passes the described test.
The treated fabric samples of Examples 43 and 44 were also evaluated for 30 water repellency using 3M Water Repellency Test V for Floorcoverings (February 1994), available from 3M Company. For this test, the treated samples were W O 97/~230 PCT~US96/06313 ç1~ çnged to penG~ ion by blends of deionized water and isopropyl alcohol (IPA).
Each blend is given a standard rating number as shown below.

Water Repellency S Ratin~ Number Water/IPA Blend o 100% Water 09/10 Water/IPA
2 80/20 "
3 70/30 "
4 60/40 "
S 50/50 "

7 30/70 "
8 20/80 "
9 l0/90 "
100% IPA

The test is run in the same manner as the oil repellency test previously described, with the reported water repellency rating co..~l,ondin~ to the highest 20 IPA-cont~ining blend for which the treated sample passes the test. The results of the water and oil repellency tests are presented in Table 10.

Table 10 Example Oil Repellency Water Rrp~

Examp1e 45 Cardboard (estim~ted to be about 200 to 240 Ib. basis) was treated with Polymer P18 and dried in an oven for 15 min--tes at 65 ~C. When oil or water was placed on the surface of an unlle~led control sample (that was also placed in the CA 02222139 1997-11-2~
W O 97/00230 PCTrUS96/06313 oven), imme~ te wetting and absorption took place within 3 seconds. When tested on the treated surface, neither water or oil wetted the surface and no absorption occurred (i.e. no dark spots developed) even after 90 mimltç~, at which time the test was fii~cQlltinlle~

Various modifications and alterations of this invention will become appalen~ '' to those skilled in the art without departing from the scope and spirit of the present invention, and it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth hereinabove.

Claims (10)

Claims We claim:

1. A water-soluble and shelf-stable aqueous fluorochemical polymeric treatment comprising polymers having interpolymerized units derived from one or more, and preferably a plurality, of each of the following monomers:
(a) monomer selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, thioacrylate or meththioacrylate compounds containing a fluoroaliphatic moiety that is linked to the residue of the compound through a divalent, organic linking group;
(b) monomer selected from the group consisting of acrylic acid, methacrylic acid, carboxyalkylacrylate and carboxyalkylmethacrylate compounds;
and (c) monomer selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, thioacrylate or meththioacrylate compounds containing an oxyalkylene or polyoxyalkylene group linked to the residue of the compound through an oxygen, sulfur or nitrogen atom.

2. A water-soluble and shelf-stable aqueous fluorochemical polymeric treatment comprising polymers having interpolymerized units derived from one or more, and preferably a plurality, of each of the following monomers:
(a) monomer selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, thioacrylate or meththioaclylate compounds containing a fluoroaliphatic moiety that is linked to the residue of the compound through a divalent, organic linking group;
(b) monomer selected from the group consisting of acrylic acid, methacrylic acid, carboxyalkylacrylate and carboxyalkylmethacrylate compounds;
(c) monomer selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, thioacrylate or meththioacrylate compounds containing an oxyalkylene or polyoxyalkylene group linked to the residue of the compound through an oxygen, sulfur or nitrogen atom; and (d) monomer selected from the group consisting of acrylate, methaclylate, acrylamide, methacrylamide, thioacrylate and meththioacrylate, compounds that contain a alkoxysilane moiety linked to the residue of the compound through a divalent organic group.

3. A waler-soluble fluorochemical polymer comprising the formula:

wherein:
R is hydrogen or an aliphatic group having from 1 to 4 carbon atoms;
Rf is a fluoroaliphatic group having a perfluorinated carbon chain from 3 to 20 carbon atoms in length;
R1 is an organic divalent connecting group;
X is independently selected as oxygen, nitrogen, or sulfur;
R2 is a short chain alkylene group;
m is 0 or 1;
M+ is a mono- or multivalent cation;
ROA is an oxyalkylene- or polyoxyalkylene-containing group;
R3 is an organic divalent connecting group;
R4 is hydrogen, or a methyl, ethyl, or butyl group; and a,b,c, and d are ~ 1.

4. The composition of claim 3 wherein:
R1 is selected from the group consisting of -CyH2y-, -CON(R5)CyH2y-, -SO2N(R5)CyH2y-, or -CyH2ySO2N(R5) CyH2y-, where R5 is hydrogen, or a methyl, ethyl, propyl, or butyl group and y is independently selected as between 1 and 6 inclusive;
ROA is an oxyalkylene or a polyoxyalkylene group of the formula -(C2H4O)p(C3H6O)q(C4H8O)rR6 where R6 is hydrogen or an alkyl group having from 1 to 4 carbon atoms or an aryl group and where p, q, or r can be zero, but their sum, p+q+r, must be a number greater than or equal to 1; and R3 is a methyl, ethyl, propyl, or butyl group.

5. A water-soluble fluorochemical polymer comprising the formula:

wherein:
R is hydrogen or an aliphatic group having from 1 to 4 carbon atoms;
Rf is a fluoroaliphatic group having a perfluorinated carbon chain from 3 to 20 carbon atoms in length;
R1 is an organic divalent connecting group;
X is independently selected as oxygen, nitrogen, or sulfur;
R is a short chain alkylene group;

m is 0 or 1;
M+ is a mono- or multivalent cation;
ROA is an oxyalkylene- or polyoxyalkylene-containing group; and a, b, and c are ~ 1.

6. The composition of claim 5 wherein:
R1 is selected from the group consisting of -CyH2y-, -CON(R5)CyH2y-, -SO2N(R5)CyH2y-, or -CyH2ySO2N(R5) CyH2y-, where R5 is hydrogen, or a methyl, ethyl, propyl, or butyl group and y is independently selected as between 1 and 6 inclusive; and ROA is an oxyalkylene or a polyoxyalkylene group of the formula -(C2H4O)p(C3H6O)q(C4H8O)rR6 where R6 is hydrogen or an alkyl or aryl group having from 1 to 4 carbon atoms and where p, q, or r can be zero, but their sum, p+q+r, must be a number greater than or equal to 1.

7. The composition according to any one of claims 1-6 wherein the polymer has a number average molecular weight between about 3500 and about 30,000 and a molecular weight distribution of greater than 1.5.

8. A shelf-stable aqueous solution comprising the composition of any one of claims 1-7.

9. A method for rendering a porous substrate repellent to water and oil-based stains comprising applying to the substrate the composition of any one of claims1-7, allowing the composition to penetrate the surface of the article, and allowing the composition to cure on the substrate surface.

10. A porous substrate treated with the composition of any one of claims 1-7.