FLUORINATED COPOLYMERS

FIELD OF THE INVENTION

This invention relates to copolymers for imparting stain resistance, oil and water repellency for hard substrates and fibrous substrates comprising a copolymer of fluorinated methacrylate, carbonate

methacrylate and methacrylic acid or salt thereof.

BACKGROUND OF THE INVENTION

Hard surface substrates such as stone, masonry, concrete, unglazed tile, brick, porous clay and various other substrates and fibrous substrates such as woven and nonwoven fibers, yarns, fabrics, fabric blends, textiles, nonwovens, paper, leather, rugs and carpets are used decoratively and functionally in indoor and outdoor environments. When untreated, these materials are susceptable to staining from water, oil, and foodstuffs such as kethcup, mustard, coffee, cooking oils, wine, and beverages. Several products exist in the marketplace for treating these substrates. Stone and tile treatment products are commonly a copolymer of a fluorinated monomer providing stain release and oil repellency, with a non-fluorinated monomer, for water repellency.

Linert et al., in WO199700230, describe a composition comprising fluoroaliphatic groups, carboxyl contianing groups, oxyalkene groups and optionally silyl groups which provide repellency to oil- and water-based stains for porous substrates.

Ueda et al., in US20070197717, describe a masonry treating agent comprising fluoromonomer, a monomer having at least one acid group, and a non-fluorinated monomer having a hydrophobic group.

What is needed are coating copolymers that provide superior performance for stain resistance, oil and water repellency to hard substrates as well as fibrous substrates. Additionally, copolymers that are modified to be dispersed in either organic or aqueous solvents are desired. The present invention meets these needs. SUMMARY OF THE INVENTION The present invention comprises copolymers of formula (I)

R _f

wherein

Rf is C2 to C-| o fluoroalkyl, optionally interrupted by one

O-, -CH2-, -CFH-, or combinations thereof; n is an integer from 1 to 10;

A is a linear, branched, or cyclic carbonate of formula

- ⁰ ~( ^CH 2)m— _j wherein m is 1 to 10 and R2 is a Ci to Cio linear, branched or cylic alkyl or aryl;

M ⁺ is H ⁺ , NH ₄ ⁺ , Na ⁺ , Li ⁺ , Cs ⁺ , K ⁺ , or mixtures thereof; a is 20 to 80 mol %;

b is 5 to 80 mol %; and

c is 0 to 70 mol %;

wherein the sum of a + b + c is equal to 100%.

The present invention further comprises a method of treating a substrate comprising contacting said substrate with a copolymer of Formula I. The present invention further comprises a substrate treated in accordance as the above mentioned method.

DETAILED DESCRIPTION

Herein, trademarks are shown in upper case.

The present invention comprises copolymers of formula (I)

R _f

wherein

Rf is C2 to Cio fluoroalkyl, optionally interrupted by one or more O-, -CH2-, -CFH-, or combinations thereof; n is an integer from 1 to 10;

A is a linear, branched, or cyclic carbonate of formula -o-(CH ₂ ) _m — _ _{wherein m} j _s 1 to 10 and R2 is a Ci to CI Q linear, branched or cylic alkyl or aryl;

M ⁺ is H ⁺ , NH4 ⁺ , Na ⁺ , Li ⁺ , Cs ⁺ , K ⁺ , or mixtures thereof; a is 20 to 80 mol %;

b is 5 to 80 mol %; and

c is 0 to 70 mol %;

wherein the sum of a + b + c is equal to 100%. In all embodiments of the present invention, a, b, and c represent the molar percentage of each individual component that is used to prepare the copolymers of the present invention. The copolymers of Formula I are present in a random order of monomers within the copolymer, represented by the dotted lines. The molar percentage of each reactant (a, b, and c) are chosen such that they are equal too any individual number within the previously specified molar range, and the sum of the combined

components is equal to 100%. One skilled in the art can easily choose molar percentages for each monomer within the stated ranges so that the total equals 100%. For example, a is any of 20, 21 , 22, 23 and so on, up to 80; b is 5, 6, 7, 8, and so on up to 80; and c is 0, 1 , 2, 3, 4 and so on up to 70. The combination of any individual value for a from 20 to 80, any individual value for b from 5 to 80, and any individual value for c from 0 to 70, that totals 100 is included within the present invention.

In particular embodiments described below, a, b, and c are each equal to any individual value within the cited range for a, b, and c respectively and the invention includes any combination of the individual valuesfor a, b, and c that total to 100.

In one embodiment, the present invention comprises copolymers of Formula I,

R wherein

Rf is C2 to Cio fluoroalkyl, optionally interrupted by one or more O-, -CH2-, -CFH-, or combinations thereof; n is an integer from 1 to 10; A is a linear, branched, or cyclic carbonate of formula or ^R " ^{0 c 0 (C h|} 2)m _t wherein m is 1 to 10 and R ² is a Ci to C^ Q linear, branched or cylic alkyl or aryl;

M ⁺ is H ⁺ ;

a is 20 to 80 mol %;

b is 20 to 80 mol %; and

c is 0 mol %.

For the first embodiment, Rf is preferably C4 to Cs perfluoroalkyl, more preferably Rf is CQ perfluoroalkyl. Preferably n is 2 to 6, more preferably n is 2. Preferably a is 30 to 70 mol %, b is 30 to 70 mol % and c is 0 mol %, more preferably a is 40 to 60 mol %, b is 40 to 60 mol %, and c is 0 mol%, most preferably a is 50 mol %, b is 50 mol %, and c is 0 mol %. Preferably A is a cyclic carbonate cyclic carbonate of formula Preferably, A is a linear or branched carbonate of

o formula ^{r2 0 c 0} ( ^{C H} 2)m , wherein m is 1 to 10 and R ² is a C-| to

o

Cio- Preferably, A is a linear carbonate of formula ^r2_0 ~ ^c— °~( ^{C H} 2)m wherein m is 1 to 10 and R ² is a Ci to Cio- Preferably, A is a branched

o carbonate of formula ^r2-0 ~ ^{c— 0—} ( ^{C H} 2) _{m j} wherein m is 1 to 10 and R ² is a Ci to C-io- Preferably m is 2 to 8, more preferably, m is 2 to 6.

Preferably R ² is a C2 to Cs; more preferably, R ² is a C2 to CQ. In a second embodiment, the present invention comprises copolymers of formula (I)

R wherein

Rf is C2 to Ci o fluoroalkyl, optionally interrupted by one or more - O-, -CH2-, -CFH-, or combinations thereof; n is an integer from 1 to 10;

A is a linear, branched, or cyclic carbonate of formula

° o) _or R ₂ _ o c L o _ (CH ₂ ) _m _ wherein m is 1 to 10 and R2 is a Ci to Ci o linear, branched or cylic alkyl or aryl;

M ⁺ is H ⁺ ;

a is 20 to 60 mol %;

b is 5 to 50 mol %; and

c is 25 to 70 mol %.

For the second embodiment, Rf is preferably C4 to Cs

perfluoroalkyl, more preferably Rf is CQ perfluoroalkyl. Preferably M ⁺ is

H ⁺ . Preferably n is 2 to 6, more preferably n is 2. Preferably a is 15 to 50 mol %, b is 15 to 40 mol % and c is 25 to 60 mol % , more preferably a is 30 to 45 mol %, b is 10 to 35 mol %, and c is 30 to 45 mol %. Preferably A is a cyclic carbonate cyclic carbonate of formula

Preferably, A is a linear or branched carbonate of formula

o

R2-0-C— o-(CH ₂ ) _m — _ herein m is 1 to 1 0 and R ² is a Ci to CI Q.

o

Preferably, A is a linear carbonate of formula ^{r2— 0-c—} °~( ^CH 2)m _j wherein m is 1 to 1 0 and R ² is a Ci to CI Q- Preferably, A is a branched o carbonate of formula ^r2-0-c— °— (CH ₂ ) _{m j} wherein m is 1 to 1 0 and R ² is a Ci to C-| o- Preferably m is 2 to 8, more preferably, m is 2 to 6.

Preferably R ² is a C2 to Cs; more preferably, R ² is a C2 to CQ.

In a third embodiment, the present invention comprises copolymers of formula (I)

R wherein

Rf is C2 to C1 0 fluoroalkyl, optionally interrupted by one or more O-, -CH2-, -CFH-, or combinations thereof; n is an integer from 1 to 10; A is a linear, branched, or cyclic carbonate of formula _or R o c o (CH ₂ ) _m _ wherein m is 1 to 10 and R2 is a Ci to CI Q linear, branched or cylic alkyl or aryl;

M ⁺ is NH ₄ ⁺ , Na ⁺ , Li ⁺ , Cs ⁺ , K ⁺ , or mixtures thereof; a is 20 to 60 mol %;

b is 5 to 50 mol %; and

c is 25 to 70 mol %.

For the third embodiment, Rf is preferably C4 to C8 perfluoroalkyi, more preferably Rf is CQ perfluoroalkyi. Preferably M ⁺ is NH4 ⁺ .

Preferably M ⁺ is Na ⁺ . More preferably M ⁺ is a mixture of NH4 ⁺ and Na ⁺ .

Preferably n is 2 to 6, more preferably n is 2. Preferably a is 15 to 50 mol %, b is 15 to 40 mol % and c is 30 to 60 mol % , more preferably a is 30 to 45 mol %, b is 10 to 35 mol %, and c is 30 to rably A is a

cyclic carbonate cyclic carbonate of formula rably

A is a linear or branched carbonate of formula

wherein m is 1 to 10 and R^ is a Ci to CI Q- Preferably, A is a linear

o carbonate of formula R ² -0-C— O— (CH ₂ ) _m — wherein m is 1 to 10 and R^ is a C to Ci o- Preferably, A is a branched carbonate of formula

o

R ² -0-C— O— (CH ₂ ) _m — wherein m is 1 to 10 and R^ is a C to CI Q- Preferably m is 2 to 8, more preferably, m is 2 to 6. Preferably R ² is a C2 to Cs, more preferably, R ² is a C2 to CQ.

In all embodiments of the present invention, a, b, and c represent the molar percentage of each individual component that is used to prepare the copolymers of the present invention. The molar percentage of each reactant (a, b, and c) are chosen such that they within the previously specified molar range and the sum of the combined components is equal to 100%. One skilled in the art can easily choose molar percentages for each monomer within the stated ranges so that the total equals 100%.

Copolymers of the present invention are prepared by radical polymerization by contacting fluorinated methacrylate monomers, carbonate methacrylate monomers, and optionally methacrylate acid monomers or salts thereof together in the presence of a radical initiator.

Copolymers of Formula I are prepared via polymerization and are carried out in the presence of one or more radical initiators. The radical initiators are present at 0.1 to 2.0 weight percent relative to the weight of the monomers employed. Initiators which may be used are peroxides such as, for example, benzoyl peroxide, lauroyl peroxide, succinyl peroxide and tert-butyl perpivalate, or azo compounds such as 2, 2'- azobisisobutyronitrile, 4,4'-azobis(4-cyanopentanoic acid) and

azodicarbonamide. Such azo initiators are commercially available from E. I. du Pont de Nemours and Company, Wilmington, DE, under the name of "VAZO" 67, 52 and 64, and by Wako Pure Industries, Ltd., Osaka, Japan, under the name "V-501 ". The process may also be performed in the presence of UV radiation and photo-initiators such as benzophenone, 2- methylanthraquinone or 2-chlorothioxanthone.

The reaction temperature varies within a wide range, that is to say between room temperature and the boiling point of the reaction mixture. The process is preferably performed between about 50°C and about 90°C, more preferably at 60 to 80°C. For copolymers of the third embodiment wherein M ⁺ is NH4 ⁺ , Na ⁺ ,

Li ⁺ , Cs ⁺ , K ⁺ , or mixtures thereof, the salt is formed by added the respective base to the polymerized polymer. For example, to form copolymers of Formula I wherein M ⁺ is NH4, one mole equivalent of ammonia is added to the reaction relative to the moles of methacrylate acid monomer used. For copolymers wherein M ⁺ is K ⁺ , one mole equivalent or more of potassium hydroxide is added. Examples of suitable bases include, but not limited to, ammonia, ammonium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide potassium hydroxide, or mixtures thereof.

The fluorinated methacrylate monomers used to prepare

copolymers of Formula I are of formula (II)

wherein Rf is C2 to C10 fluoroalkyl, optionally interrupted by one or more -O-, -CH2-, -CFH-, or combinations thereof, n is an integer from 1 to 10, and R1 is H or CH3. Examples of Rf include, but are not limited to,

CF ₃ (CF ₂ )x-, CF ₃ (CF2)x(CH ₂ CF2) _y -, CF ₃ (CF2) _y O(CF ₂ ) _y -, and

CF3(CF2) _y OCFH(CF2) _z - _> wherein each x is independently 1 to 9, each y is independently 1 to 3, and each z is independently 1 to 4. Preferably, Rf is C4 to Cs fluoroalkyl, more preferably, Rf is CQ fluoroalkyl. Preferably, n is 2 to 6, more preferably n is 2.

Fluorinated (meth)arcylates of Formula (II), are synthesized from the corresponding alcohols. These fluorinated methacrylate compounds are prepared by either esterification of the corresponding alcohol with acrylic acid or methacrylic acid or by tranesterification with methyl acrylate or methyl methacrylate. These preparations are well known and are described in U.S. Patent 3,282,905, herein incorporated by reference.

Fluorinated (meth)arcylates useful in the present invention are prepared from alcohols having the formula CF3(CF2) _x (CH2) _n OH wherein each x is individually 1 to 9 and n is an integer from 1 to 10, are

commercially available from E. I. du Pont de Nemours and Company, Wilmington, DE. These alcohols are also be prepared by reaction of the corresponding perfluoroalkyl iodies with oleum and hydrolyzed according to the procedure described in WO 95/1 1877, herein incorporated by reference. These alcohols are available as a homologue distribution mixture or are fraction distilled into individual chain lengths.

Fluorinated (meth)acrylates useful in the present invention are prepared from alcohols having the formula

CF3(CF2)x(CH2CF2)p(CH2)nOH wherein each x is independently 1 to 4, each p is independently 1 to 2, and n is an integer from 1 to 10. These alcohols are prepared by the telomerization of perfluoroalkyl iodides with vinylidene fluoride followed by ethylene insertion. A detailed description of the vinylidene fluoride reaction is described in Balague, et al., "Synthesis of Fluorinated telomers, Part 1 , Telomerization of vinylidene fluoride with perfluoroalkyl iodides", J. Fluor. Chem. (1995), 70(2), 215-23. Reaction details for the ethylene insertion reaction are described in U.S. Patent 3,979,469. The alcohol is prepared with oleum and hydrolysis as described above.

Fluorinated (meth)arcylates useful in the present invention are prepared from alcohols having the formula CF3(CF2)yO(CF2)y(CH2) _n OH wherien each y is independently 1 to 3 and n is an integer of 1 to 10.

These alcohols are prepared from the corresponding perfluoroalkyl ether iodides, of formula CF3(CF2)yO(CF2)yl wherien each y is independently 1 to 3. These iodides are prepared according to the procedure described in U.S. Patent 5,481 ,028, hereby incorporated by reference, by reacting a perfluorovinyl ether with ICI/HF and BF3. Ethylene insertion and alcohol conversion is as described above. The carbonate methacrylate monomers used to prepare

copolymers of Formula I are of formula II

o

R ² -0-C— O— (CH ₂ ) _m — wherein m is 1 to 10 and is a Ci to Cio linear branched or cylic alkyl or aryl. These carbonates useful in the present inveniton are prepared by reacting an organic carbonates containing an alcohol group with with (meth)acryloyl chloride in the presence of a halogen acceptor, such as an amine. Alternatively, alkyl chloroformate are reacted with hydroxyalkyi acrylates in the presence of a halogen acceptor. Synthesis of carbonates useful in the present invention are described by Chen, in U.S. Patent 4,344,982. Synthesis of cyclic carbonates useful in the present invention are described by D'Alelio et al, in "Preparation and Polymerization of Some Vinyl Monomers Containing the 2-Oxo-1 ,3- Dioxolane Group" Journal of Polymer Science: Part A-1 (1967), Vol. 5, 307-321 .

The copolymers of Formula I are preferably in the form of a dispersion. It is typically employed as a solvent dispersion or an aqueous dispersion. For the first embodiment, copolymers of Formula I wherein a is 20 to 80 mol %, b is 20 to 80 mol %, and c is 0 mol %, the dispersions are preferably prepared in organic solvents, such as tetrahydrofuran, or as an aqueous dispersion. In the second embodiment, wherein M ⁺ is H, a is 20 to 60 mol %; b is 5 to 50 mol %; and c is 25 to 70 mol %, the

dispersions are preferably prepared in organic solvents, such as tetrahydrofuran, or as an aqueous dispersion with one or more

surfactants. For the third embodiment, wherein M ⁺ is NH4 ⁺ , Na ⁺ , Li ⁺ ,

Cs ⁺ , or K ⁺ , or mixtures thereof, a is 20 to 60 mol %; b is 5 to 50 mol %; and c is 25 to 70 mol %, dispersions are preferably prepared in water.

Surfactants useful in the present invention, such as in the first and second embodiments, are any of those surfactants commonly used to prepare aqueous dispersions. Examples of suitable surfactants are methyl chloride salt of an ethoxylated alkyi amine salt, such as an 18- carbon alkylamine with 15 moles of ethylene oxide and condensation products of ethylene oxide with Ci 2 to Ci Q fatty alcohols; Ci 2 to Ci Q fatty acids; alkyi phenols having 8 to 18 carbon atoms in the alkyi group; C12 to C18 alkyi thiols and C12 to Ci s alkyi amines. Preferred examples of suitable surfactants are commercially available as ETHOQUAD 18/25 available from Akzo Nobel, Chicago, IL and as TWEEN 20, available from Sigma Aldrich, St. Louis, MO.

The present invention further comprises a method of treating a substrate to provide stain resistance, oil and water repellency comprising contacting the substrate surface with a copolymer of Formula I. The copolymers of the present invention are in the form of an organic dispersion or an aqueous dispersion and can optionally contain one or more surfactants. The dispersions are added alone or can optionally include additives or treatment agents. The copolymers of the present invention are applied to substrates by known means, including but not limited to, brushing, spraying, rollering, dipping, padding, doctor blade, wipe, dip techniques, and wet-on-wet procedure. Those skilled in the art undertsand that the type of substrate; i.e., hard surface or textile, will determine the appropriate mode of application. For example, for a hard surface such as tile, application of copolymers are applied by brushing or spraying. For fibrous substrates, such as cottons or nylons, padding or dipping are choosen to apply the copolymers to the substrate. The present invention further comprises one or more substrates treated according to the method of the present invention. These substrates comprise hard surface substrates or fibrous substrates.

Examples of hard surface substrates include, but are not limited to, unglazed concrete, brick, tile, stone such as limestone and saltillo, grout, mortar, composite materials such as terrazzo, wall and ceiling panels including those fabricated with gypsum board, marble, statuary, monuments, and wood. Suitable fibrous substrates include, but are not limited to, woven and nonwoven fibers, yarns, fabrics, fabric blends, textiles, nonwovens, paper, leather, rugs and carpets. These are made from natural or synthetic fibers including cotton, cellulose, wool, silk, polyamide, polyester, polyolefin, polyacrylonitrile, polypropylene, rayon, nylon, aramid, and acetate. The treated substrates have improved repellency to water, oil and greases and provide protection against staining.

The copolymers, methods, and treated substrates of the present invention are useful in providing stain resistance and water and oil repellency to a variety of substrates. The copolymers are easily adaptable for a variety of applications and are used as organic or aqueous

dispersions and optionally contain one or mors surfactants. The copolymers also provide stain resistance after washing cycles.

EXAMPLES

MATERIALS AND TEST METHODS

Cyclic Carbonate Methacrylate Preparation

A cyclic carbonate methacrylate, 2-methyl acrylic acid 2-oxo-[1 ,3]- dioxolan-4-ylmethyl ester, was prepared by reacting 4-hydroxymethyl-1 , 3- dioxolan-one (10.164 g, 84 mmol, comercially available from

SigmaAldrich, St. Louis, MO), triethylamine (9.27 g, 92 mmol), and ethyl acetate (100 mL) in a three-neck flask equipped with a magnetic stir bar and was purged constantly by nitrogen. The flask was immersed in an ice water bath to maintain the reaction temperature below 5°C. Methacryloyl chloride solution (9.445 g, 91 mol in 20 mL acetate) was slowly added to the reaction mixture over an hour and a half, and methoxy phenyl (0.002 grams) was added and reacted overnight at room temperature. The resulting product (triethylamine salt) was subsequently removed via vacuum assisted filtration. The resultant product was washed three times with saturated sodium bicarbonate solution, three times with 1 wt% aqueous hydrochloric acid solution, and three times with saturated sodium chloride solution, followed by drying overnight over sodium sulfate. After the sodium sulfate was removed via vacuum assisted filtration, the solvent was removed via rotary evaporation to give 2-methyl acrylic acid 2-oxo- [1 ,3]-dioxolan-4-ylmethyl ester (12.4 g, 67 mmol). This cyclic carbonate methacryalte was used to prepare the following examples 1 though 8.

Linear Carbonate Methacrylate Prepartion

ω-Methoxycarbonyloxyethyl methacrylate monomer was prepared according to Example 17a in Fischer and Eisenbach, in Makromol. Chem., Rapid Commun. 9, 503 - 51 1 by reacting 2-hydroxyethylmethacrylate (10 g, 76.8 mmol), methyl chloroformate (10.89 g, 1 15.2 mmol) and Triethyl amine (8.78 g, 86.8 mmol in 100 ml_ methylene chloride at -70 °C under nitrogen. The reaction mixture was warmed to room temperature overnight. The reaction mixture was then diluted with additional methylene chloride and washed with water, followed by washes of hydrochloric acid (1 N), sodium carbonate (1 N), and water again. The resulting mixture, ω-methoxycarbonyloxyethyl methacrylate along with unreacted 2-hydroxylethylmethacrylate (9.35 g) was used to prepare example 9.

Application and Testing of Polymers on Stone Tile surface

The copolymers of the present invention were applied as

dispersions and tested on limestone and saltillo stone tiles. The stone tiles are wiped with a damp SONTARA wipe (commercially available from E. I. du Pont de Nemours and Company, Wilmington, DE). The stones dried overnight at room temp and sectioned into 9 equal segments by adhesive tape. The copolymers of the present invention were applied as dispersions to each section using a bristle brush. The amount of polymer applied was determined by taking the weight difference of the polymer stock solution before and after applicatin. Each section was brushed with a dispersion to form one even coat. Typically four main brush passes were used to cover the surface. After 15 minutes, any excess copolymer on the surface, was removed by buffing the surface with a wipe. The coating was allowed to dry overnight and then performance was evaluated by the test methods described below.

Application onto Textile Fabrics:

Textile fabric was treated with the fluorinated polymer solutions using the following process. Polymer solutions were prepared in tetrahydrofuran to contain 2000 mg/kg of fluorine. The solutions were applied to fabric substrates by pipetting the polymer solution onto substrates to saturation. After application, the substrate was dried in air and cured at approximately 150°C for about 2 minutes. The substrate was allowed to cool to room temperature then performance evaluated by the test methods described below.

Washability Testing

The washability of the copolymers of the present invention was tested on tiles to evaluate the copolymers ability to retain satin reistance and oil and water repellency after cleaning. The treated tiles were tested according to the 24-Hour Stain Testing listed below for stain resistence. The treated tiles were first washed with water and scoured with a sponged wrapped in nylon netting for ten passes, rinsed with plain water and allowed to dry for 24 hours and tested for stain resistence. In a separate section of the tile, the treated tile was washed with soap and water and scoured with a sponged wrapped in nylon netting for ten passes, rinsed with plain water and allowed to dry for 24 hours and tested for stain resistence.

Test Method 1 . Water and Oil Beading Test

Individual drops of water and vegetable oil (approximately 4 to

5 mm in diameter or 0.04 to 0.05 ml_ volume) were placed on the coated surface using a glass pipette. The drop was allowed to sit on the surface for five minutes and the degree of beading (i.e., contact angle) was visually determined. The degree of beading is rated from 0 to 5 as shown in the Table 1 below. Higher ratings are indicative in superior repellency performance.

Table 1 . Water and Oil Contact Angle Measurments

Test Method 2. 24-Hour Stain Testing:

One drop each of common household stains (mustard, ketchup, vegetable oil, coffee) were individually placed on the treated tile surface and allowed to sit for 24 hours. The stains were removed by washing with water and a nylon bristle brush. The treated stone was allowed to dry at room temperature (72 to 78°F) until the stone was completely dry

(approximately 12 to 24 hours). The stain residue remaining on the tile surface was visually rated from 0 to 4 as follows. Liquid stains that does not leave a visible surface stain but penetrates deep into the substrate are given a rating 4. Lower rating indicates better performance. The stain procedure was repeated 4 times and averaged. Table 2. 24-Hour stain ratings

A stain score aggregate is calculated by adding the sum of all stain scores for a test sample and the performance compared with the total maximum possible score (i.e., for 4 stains, the highest rating is 16).

Test Method 3 - Water Repellencv Test

The water repellency of treated stone tile substrates and fibrous substrates was measured according to AATCC (American Association of Textile Chemists and Colorists) standard Test Method No. 193-2004. The test determined the resistance of the treated substrate to wetting by aqueous test solutions (see Table 3 for Test Solution copolymers). Drops of test solutions (approximately 5 mm in diameter or 0.05 ml_ volume) of water-alcohol mixtures of varying surface tensions were placed on the treated substrate and the extent of surface wetting was determined visually. Three drops of test solution #1 were placed on the substrate. After 10 seconds, the drops were removed by using vacuum aspiration. If no liquid penetration or partial absorption (appearance of a darker wet patch on the substrate) was observed, the test was repeated with Test Liquid 2 and with progressively higher Test Liquid numbers until liquid penetration (appearance of a darker wet patch on the substrate) was observed. The rating was the highest Test Liquid number that did not penetrate into the substrate. Higher scores indicate greater water repellency and superior performance.

The composition of water repellency test liquids is shown Table 3 below.

Table 3.

Test Method 4. Oil Repellency Test

The oil repellency of treated stone tile substrates and fibrous substrates was tested using a modification of AATCC standard Test Method No. 1 18, and was modified as follows. A series of organic liquids, identified below in the Table 4, were applied drop wise to the substrate. Beginning with the lowest numbered test liquid (Repellency Rating No. 1 ), one drop (approximately 5 mm in diameter or 0.05 mL volume) was placed on each of three locations at least 5 mm apart. The drops were observed for 30 seconds. If, at the end of this period, two of the three drops were still spherical in shape with no wicking around the drops, three drops of the next highest numbered liquid were placed on adjacent sites and similarly observed for 30 seconds. The procedure was continued until one of the test liquids results in two of the three drops failed to remain spherical to hemispherical, or wetting or wicking occurs.

The oil repellency rating was the highest numbered test liquid for which two of the three drops remained spherical to hemispherical, with no wicking for 30 seconds. Higher scores indicate greater oil repellency.

Table 4.

^* NUJOL (comercially available from Plough, Inc. Memphis,

Tennesse) is a mineral oil having a Saybolt viscosity of 360/390 at 38°C and a specific gravity of 0.880/0.900 at 15°C.

EXAMPLES

Example 1

A copolymer of Formula I was prepared in organic solvent.

Perfluoroalkyl methacrylate, having the formula

CF ₃ (CF2)5CH2CH ₂ OC(O)C(CH3)=CH2 (2.846 g, 6.59 mmol,

commercially available from E. I. du Pont de Nemours and Company, Wilmington, DE), 2-methyl acrylic acid 2-oxo-[1 ,3]-dioxolan-4-ylmethyl ester monomer (2.02 g, 10.86 mmol), and tetrahydrofuran (THF, 25 g) were added to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condensor. The reaction vessel was then purged with nitrogen at room temperature (approximately 23°C) for one hour. The reaction vessel was then placed in a heated bath at 60°C and initiator (0.125 g, 0.65 mmol, VAZO 67, comercially available from E. I. du Pont de Nemours and Company, Wilmington, DE) was added to the reaction flask using a syringe. The temperature of the reaction vessel was raised to 68°C and held at 68°C for 16 hours. The molar concentration of the individual monomers are listed in Table 5. The reaction product was cooled and applied to saltillo, limestone, cotton, and nylon substrates and tested according to the methods described above.

Example 2

A copolymer of Formula I was prepared in water with surfactants. Perfluoroalkyl methacrylate, having the formula

CF ₃ (CF2)5CH2CH ₂ OC(O)C(CH3)=CH2 (1 .01 g, 2.34mmol), 2-methyl acrylic acid 2-oxo-[1 ,3]-dioxolan-4-ylmethyl ester monomer (0.751 g, 4.038 mmol), D.I. water (18.18 g) surfactants (Tween 20, 0.546 g and ethoquad 18/25, 1 .272g) were added to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condensor. The reaction vessel was then purged with nitrogen at room temperature (approximately 23°C) for one hour. The reaction vessel was then placed in a heated bath at 60°C and an aqueous solution of initiator (0.044 g, VAZO 56, comercially available from E. I. du Pont de Nemours and Company, Wilmington, DE) was added to the reaction flask using a syringe. The temperature of the reaction vessel was raised to 56°C and held for 16 hours. The molar concentration of the individual monomers are listed in Table 5. The reaction product was cooled and applied to saltillo, limestone, cotton, and nylon substrates and tested according to the methods described above.

Example 3

A copolymer of Formula I was prepared in an organic solvent wherein M ⁺ is H. Perfluoroalkyl methacrylate, having the formula

CF3(CF2)5CH ₂ CH ₂ OC(O)C(CH3)=CH2 (2.79 g, 6.45 mmol), 2-methyl acrylic acid 2-oxo-[1 ,3]-dioxolan-4-ylmethyl ester monomer (1 .0 g, 5.37 mmol), methylacrylic acid (0.462 g, 5.37 mmol) and THF (20 g) were added to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condensor. The reaction vessel was then purged with nitrogen at room temperature (approximately 23°C) for one hour. The reaction vessel was then placed in a heated bath at 60°C and a THF (1 ml_) solution initiator (0.121 g, 0.63 mmol, VAZO 67, comercially available from

E. I. du Pont de Nemours and Company, Wilmington, DE) was added to the reaction flask using a syringe. The temperature of the reaction vessel was raised to 68°C and held at 68°C for 16 hours. The molar

concentration of the individual monomers are listed in Table 5. The reaction product was cooled and applied to saltillo, limestone, cotton, and nylon substrates and tested according to the methods described above.

Examples 4 and 5

Copolymers of Formula I was prepared in organic solvent, wherein

M ⁺ is H ⁺ . The procedure of Example 3 was repeated for Examples 4 and 5 with varying amounts of perfluoroalkyl methacrylate, cyclic carbonate methacrylate, and methacylic acid in THF. The reaction product was cooled and applied to saltillo, limestone, cotton, and nylon substrates and tested according to the methods described above.

Example 6, 7, and 8

Examples 6, 7, and 8, copolymers of Formula I, wherein M ⁺ is

NH4 ⁺ , were prepared by the following procedure with the molar

concentration of the individual monomers are listed in Table 5 for each Example.

Perfluoroalkyl methacrylate, having the formula

CF3(CF2)5CH ₂ CH ₂ OC(O)C(CH3)=CH2 (2.79 g, 6.45 mmol), 2-methyl acrylic acid 2-oxo-[1 ,3]-dioxolan-4-ylmethyl ester monomer (1 .0 g, 5.37 mmol), methylacrylic acid (0.462 g, 5.37 mmol) and THF (20 g) were added to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condensor. The reaction vessel was then purged with nitrogen at room temperature (approximately 23°C) for one hour. The reaction vessel was then placed in a heated bath at 60°C and a THF (1 ml_) solution initiator (0.121 g, 0.63 mmol, VAZO 67, comercially available from E. I. du Pont de Nemours and Company, Wilmington, DE) was added to the reaction flask using a syringe. The temperature of the reaction vessel was raised to 68°C and held at 68°C for 16 hours. A warm solution mmonium hydroxide (0.394 g (6.5 mmol), 28 wt% NH ₃ ) in water (25 g) was added to the reaction mixture at 60 C and stirring continued at 60°C for 45 minutes. THF was then removed by distillation under vacuum and the resulting dispersion was diluted with water to obtain the desired

concentration. The diluted dispersion was applied to saltillo and limestone substrates and tested according to the methods described above.

Table 5. Molar concentration of monomers and solvent selection

Example 9

A copolymer of Formula I was prepared in an organic solvent wherein M is NH ⁺ . Perfluoroalkyl methacrylate, having the formula CF ₃ (CF2)5CH2CH ₂ OC(O)C(CH3)=CH2 (1 1 .15 g, 25.8 mmol), ω- methoxycarbonyloxyethyl methacrylate/hydroxymethylmethacrylate monomer (1 .445 g, 7.7 mmol), hydroxyethyl mathacrylate (0.619 g, 4.8 mmol) and methylacrylic acid (2.46 g, 28.6 mmol) in THF (75 g) were added to a nitrogen purged reaction vessel equipped with a magnetic stir bar and condensor. The reaction vessel was then purged with nitrogen at room temperature (approximately 23°C) for one hour. The reaction vessel was then placed in a heated bath at 60°C and a THF (2 mL) solution of the initiator (0.6 g, 0.293 mmol, VAZO 67, comercially available from

E. I. du Pont de Nemours and Company, Wilmington, DE) was added to the reaction flask using a syringe. The temperature of the reaction vessel was raised to 68°C and held at 68°C for 16 hours to obtain the copolymer solution in THF. 21 .5 g of the polymer solution in THF (-30% wt% in polymer in THF) was transferred to a neutralization reactor and heated to 60°C. A warm solution mmonium hydroxide (0.432 g (7.151 mmol), 28 wt% NH ₃ ) in water (25 g) was added to the reaction mixture at 60 C and stirring continued at 60°C for 45 minutes. THF was then removed by distillation and the resulting dispersion was diluted with water to obtain the desired concentration. The diluted dispersion was applied to saltillo and limestone substrates and tested according to the methods described above.

Examples 1 though 9 were applied to saltillo and limstone surfaces and tested according to Test Method 1 , Oil and Water Beading, Test Methods 3, Water repellency, and Test Method 4, Oil Repellency according to the methods as described in above. Untreated saltillo and limestone were also tested as a comparision. Results are listed below in Table 6 for Oil and Water Beading, Table 7 for Test Methods 3 and 4.

Table 6. Stone and Tile Oil and Water Beading Scores (rating 0 to 5, 5 is best)

Table 7. Stone and Tile Teflon Kit Test Scores (Oil: 0-8,

8 is best: Water: rating 0-12, 12 is best)

All of the examples performed well for oil and water beading, oil and water repellency for limestone substrates when compared to untreated stone. Examples 1 , 3 through 9 performed well for saltillo for oil and water beading, oil and water repellency compared to untreated stone.

The examples were applied to saltillo and limestone tiles and then were tested for staining according to Test Method 2 as described above. Results are listed in Tables 8 for saltillo and Table 9 for limstone.

Table 8. Stain Scoring (rating 0-4, 0 best, 4 worst or

represent deep stain penetration), Saltillo

"represent deep penetration of stain to the substrate

Table 9. Stain Scoring (rating 0-4, 0 best, 4 worst or represent deep stain penetration), Limestone

Examples 1 though 9 performed well compared when applied to saltillo and limestone compared to untreated tiles. In some cases, the stains left no visable mark, such as for vegatable oil and coffee on limestone substrates.

Example 1 through 5 were applied to cotton and nylon samples and tested according to Test Methods 3 and 4 for oil and water repellency. Results are listed in Table 10.

Table 10. Oil and Water Repellencv Ratings (rating 0-12, 12 is best)

Examples 1 , 3 though 5 performed well on the two fibrous substrates tested compared to untreated substrates. Table 1 1 . Stain Scoring after Wash Testing on Limestone

Limestone tile was treated by a copolymer of Example 4 and was tested for stain resistance 1 ) before washing, 2) after washing with water and 3) after washing with soap and water. Example 4 performed well for stain resistance on Limestone after water washing with water. The stain resistance was better than untreated after soap and water washing in all stains except mustard.