MXPA06007615A - Stain resistant grout - Google Patents

Abstract

Polymeric grout formulations comprising one or more urethane oligomers of at least two polymerized units comprising the reaction product of:(a) one or more polyfunctional isocyanate compounds;(b) one or more polyols;(c) one or more monoalcohols selected from the group consisting of fluorocarbon monoalcohols;and (d) one or more silanes. In another embodiment, the polymeric grout composition comprises an additive comprising an oligomer comprising at least two polymerized units, each said polymerized unit comprising a urethane group, and said oligomer being substituted with (i) one or more covalently bonded perfluoroalkyl groups, or one or more covalently bonded perfluoroheteroalkyl groups, and (ii) one or more covalently bonded silyl groups.

Description

STAINED RESISTANT CEMENT GROUND FIELD OF THE INVENTION The present invention relates to stain-resistant polymeric cement slurry.

BACKGROUND OF THE INVENTION Cement slurries have become well known; Illustrative examples are described in U.S. Patent Nos. 4,616,050, 4,472,540, and 3,859,233. Known polymeric cement slurry formulations are prone to staining. Common cement grout protective sealers are widely used to protect grout from staining. However, this allows an additional sealing procedure which in many cases is time consuming. However, ceramic slabs do not need any coating, therefore it is difficult to coat only the narrow cement grout. There is a need for improved cement grout formulations that will provide increased stain resistance and do not require additional protective coatings.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides the slurry of Ref. 174278 stain-resistant polymer cement. In summary, the invention provides polymeric cement slurry formulations comprising an additive comprising one or more urethane oligomers of at least two polymerized units. The oligomers comprise the reaction product of: (a) one or more polyfunctional isocyanate compounds; (b) one or more polyols; -. (c) one or more monoalcohols selected from the group consisting of fluorocarbon monoalcohols; and (d) one or more silanes of the following formula: X-R1-Si- (Y) 3 wherein X is -NH2; -SH; -OH; or -NRH, wherein R is selected from the group consisting of phenyl, straight and branched aliphatic, alicyclic, and aliphatic ester groups; R1 is an alkylene, heteroalkylene, aralkylene, or heteroaralkylene group; and Each Y is independent a hydroxyl; a hydrolyzable portion selected from the group consisting of alkoxy, acyloxy, heteroalkyloxy, heteroacyloxy, halo, and oxime; or a non-hydrolyzable portion selected from the group consisting of phenyl, alicyclic, straight chain aliphatic, and branched chain aliphatic, wherein at least one Y is a portion hydrolysable. In another aspect, the present invention provides polymeric cement slurry compositions comprising an additive comprising an oligomer comprising at least two polymerized units, each polymerized unit comprising a urethane group, and the oligomer is substituted with (i) one or more covalently linked perfluoroalkyl groups, or one or more covalently linked perfluoroheteroalkyl groups, and (ii) one or more covalently bonded silyl groups. The cement grout composition of the invention exhibits water repellency, oil repellency, and improved stain resistance.

Definitions Unless stated otherwise, the following terms used in the specification and claims have the following meanings: "Acyloxy" means a radical --OC (0) R where R is alkyl, alkenyl, and cycloalkyl, for example, acetoxy, 3, 3, 3-trifluoroacetoxy, propionyloxy, and the like. "Alkoxy" means a radical -OR where R is an alkyl group as defined below, for example, methoxy, ethoxy, propoxy, butoxy, and the like. . "Alkyl" means a linear saturated monovalent hydrocarbon radical having from one to about twelve carbon atoms or a branched saturated monovalent hydrocarbon radical having from three to about twelve carbon atoms, for example, methyl, ethyl, 1-propyl, 2-propyl, pentyl, and the like. "Alkylene" means a linear saturated divalent hydrocarbon radical having from one to about twelve carbon atoms or a branched saturated divalent hydrocarbon radical having from three to about twelve carbon atoms, for example, methylene, ethylene, propylene, 2-methylpropylene, pentylene, hexylene, and the like. "Aralkylene" means an alkylene radical defined above with an aromatic group attached to the alkylene radical, for example, benzyl, pyridylmethyl, 1-naphthylethyl, and the like. "Fluorocarbon monoalcohol" means a compound having a hydroxyl group and a perfluoroalkyl or a perfluoroheteralkyl group, for example, C4F9S? 2N (CH3) CH2CH2OH, C4F9CH2CH2OH, C2F50 (C2F40) 3CF2CONHC2H4OH, c-C6FnCH2OH, and the like. "Halo" means fluorine, chlorine, bromine, or iodine, preferably fluorine and chlorine. "Hard substrate" means any rigid material that maintains its shape, for example, glass, ceramics, concrete, natural stone, wood, metals, plastics, and Similar . "Heteroacyloxy" has essentially the meaning given above for acyloxy except that one or more heteroatoms (e.g., oxygen, sulfur, and / or nitrogen) may be present in the R group and the total number of carbon atoms present may be up to 50, for example, CH3CH2OCH2CH2C (0) 0-, C4H9OCH2CH2OCH2CH2C (0) 0-, CH30 (CH2CH20) nCH2CH2C (0) 0-, and the like. "Heteroalkoxy" has essentially the meaning given above for alkoxy except that one or more heteroatoms (eg, oxygen, sulfur, and / or nitrogen) may be present in the alkyl chain and the total number of carbon atoms present may be up to 50, for example, CH3CH2OCH2CH20-, C4H9OCH2CH2OCH2CH20-, CH30 (CH2CH20) nH, and the like. "Heteroalkyl" has essentially the meaning given above for alkyl except that one or more heteroatoms (eg, oxygen, sulfur, and / or nitrogen) may be present in the alkyl chain, these heteroatoms are separated from each other by at least one carbon, for example, CH3CH20CH2CH2-, CH3CH20CH2CH20CH (CH3) CH2-, C4F9CH2CH2SCH2CH2-, and the like. "Heteroalkylene" has essentially the meaning given above for alkylene except that one or more heteroatoms (eg, oxygen, sulfur, and / or -nitrogen) may be present in the alkylene chain, these heteroatoms are separated from each other by at least one carbon, for example, -CH2OCH20-, -CH2CH2OCH2CH2-, -CH2CH2N (CH3) CH2CH2-, CH2CH2SCH2CH2-, and the like. "-:" Heteroaralkylene "means an aralkylene radical defined above except that cathenated oxygen, sulfur, and / or" nitrogen atoms may be present, for example, phenyleneoxymethyl, phenyleneoxyethyl, benzylenyloxyethyl, and the like. "Long chain hydrocarbon monoalcohol" means a compound having a hydroxyl group and a long chain hydrocarbon group having 10 to 18 carbons which may be saturated, unsaturated, or aromatic, and optionally substituted with one or more groups chlorine, bromine, trifluoromethyl or phenyl, for example, CH3 (CH2)? 0CH2OH, CH3 (CH2)? 4CH2OH, and the like. "Oligomer" means a polymer molecule consisting of only a few (polymerized) repeating units (e.g., from 2 to about 20). "Perfluoroalkyl" has essentially the meaning given above for "alkyl" except that all or essentially all of the hydrogen atoms of the alkyl radical are replaced by fluorine atoms and the number of carbon atoms is preferably from 2 to about 6, for example, perfluoropropyl, perfluorobutyl, perfluorohexyl, and the like. "Perfluoroalkylene" has essentially the meaning given above for "alkylene" except that all or essentially all of the hydrogen atoms of the alkylene radical are replaced by fluorine atoms, for example, perfluoropropylene, perfluorobutylene, perfluorooctylene, and the like. "Perfluoroheteroalkyl" has essentially the meaning given above for "heteroalkyl" except that all or essentially all of the hydrogen atoms of the heteroalkyl radical are replaced by fluorine atoms and the number of carbon atoms is from 3 to about 100, for example, CF3CF2OCF2CF2 -, CF3CF20 (CF2CF20) 3CF2CF2-, C3F70 (CF (CF3) CF20) mCF (CF3) CF2- where m is from about 10 to about 30, and the like. "Perfluoroheteroalkylene" has essentially the meaning given above for "heteroalkylene" except that all or essentially all of the hydrogen atoms of the heteroalkylene radical are replaced by fluorine atoms, and the number of carbon atoms is from 3 to about 100, for example, -CF2OCF2_, -CF20 (CF20) n (CF2CF20) mCF2-, and the like. "Perfluorinated group" means an organic group in which all or essentially all of the hydrogen atoms attached to carbon are replaced with fluorine atoms, by example, perfluoroalkyl, perfluoroheteroalkyl, and the like. "Polyfunctional isocyanate compound" means a compound that contains two or more isocyanate radicals, -NCO, attached to a multivalent organic group, for example, hexamethylene diisocyanate, the biuret and isocyanurate of hexamethylene diisocyanate, and the like. "Polyol" means an organic compound or polymer with an average of at least about 2 primary or secondary hydroxyl groups per molecule, for example, ethylene glycol, propylene glycol, 1,6-hexanediol, and the like. "Polyalkylsiloxane diol" means a molecule having two hydroxyl groups and a repeating unit with the structure, - (Si (R) 20) -, for example, HOR [Si (CH3) 20] nSiR0H, wherein each R is independently straight chain or branched alkyl. "Dio! Polyarylsiloxane" means a molecule having two hydroxyl groups and a repeating unit with the structure, - (Si (Ar) 20) -, for example, HOR [Si (C6H5) 2Oj SiROH, wherein each R is independently straight chain or branched alkyl. "Repellency" is a measure of a resistance of the substrate treated to moisture adhesion of oil and / or water and / or adhesion of particulate earth. The repellency can be measured by the test methods described herein.

"Resistance", in the context of soiling or staining, is a measure of the capacity of the treated substrate to avoid staining and / or dirtiness when it comes in contact with stains or dirt respectively. "Release" is a measure of the ability of the treated substrate to have dirt and / or stain removed by cleaning or washing. "Silane group" means a group comprising silicon to which at least one hydrolyzable group - is attached, for example, - Si (OCH3) 3, -Si (OOCCH3) 2CH3, -Si (Cl) 3, and the like.

DETAILED DESCRIPTION OF ILLUSTRATIVE MODALITIES Additives The polymeric cement slurry additives of the present invention comprise one or more stabilized urethane oligomers having at least two polymerized units. The polymerized units are selected from the group consisting of fluorine-containing urethane oligomers. This oligomer comprises the reaction product of (a) one or more polyfunctional isocyanate compounds, (b) one or more polyols, (c) one or more monoalcohols selected from the group consisting of fluorochemical monoalcohols, (d) one or more silanes , and optionally (e) one or more stabilizers selected from the group consisting of UV absorbers comprising one or more groups that react with isocyanate and HALS comprising one or more reactive isocyanate groups. Preferably, the oligomer further comprises the reaction product of (f) one or more water solubilizing compounds comprising one or more water solubilizing groups and at least one reactive isocyanate hydrogen-containing group. The silanes are of the following formula: X-Rx-Si- (Y) 3 wherein: X is -NH2; -SH; -OH; or -NRH, wherein R is a phenyl, straight or branched aliphatic, alicyclic, or aliphatic ester group; R1 is an alkylene, heteroalkylene, aralkylene, or heteroaralkylene group; and each Y is independently a hydroxyl; a hydrolyzable portion selected from the group consisting of alkoxy, acyloxy, heteroalkyloxy, heteroacyloxy, halo, and oxime; or a non-hydrolyzable portion selected from the group consisting of phenyl, alicyclic, straight chain aliphatic, and branched chain aliphatic, wherein at least one Y is a hydrolysable portion. The oligomer comprises at least two polymerized units. Each polymerized unit comprises a urethane group which is derived or derivable from the reaction of at least one polyfunctional isocyanate compound and at least one polyol. The oligomer comprises one or more of the following covalently linked to the polymerized units of the oligomer: (i) one or more perfluoroalkyl groups, one or more perfluoroheteroalkyl groups; (ii) one or more silyl groups; and (iii) one or more stabilizer portions. These groups can be pendants from the skeleton or the polymerized or terminal unit. The "oligomer may further comprise one or more covalently linked water solubilization groups, these solubilization groups independently being pendent from the polymerized or terminal unit In a preferred embodiment, additives of the present invention comprise a mixture of urethane resulting from the reaction of (a) one or more polyfunctional isocyanate compounds, (b) one or more polyols, (c) one or more fluorochemical monoalcohols, (d) one or more silanes as described above, and optionally ( e) one or more stabilizers comprising one or more groups that react with isocyanate In another preferred embodiment, the chemical composition of the present invention comprises a mixture of urethane molecules resulting from the reaction of (a) one or more compounds of polyfunctional isocyanate, (b) one or more polyols, (c) one or more fluorochemical monoalcohols, (d) one or more silanes as described above, (e) (optionally) one or more stabilizers "selected from the group consisting of UV absorbers comprising one or more reactive isocyanate groups and HALS comprising one or more reactive isocyanate groups, and (f) one or more water solubilization compounds comprising one or more water solubilization groups and at least one reactive isocyanate hydrogen-containing group The water solubilization compounds of the present invention may be represented generally by "W-Rx-X", wherein it is one or more water solubilization groups, X is a reactive isocyanate group such as -NH2; -SH; -OH; or -NRH-, where R is a phenyl, straight or branched aliphatic, alicyclic or aliphatic ester group; and R1 is an alkylene, heteroalkylene, aralkylene, or heteroaralkylene group. The composition may further contain fluorine-containing urethane compounds having less than two polymerized units. The mixture of urethane molecules preferably comprises urethane molecules having a variant number of polymerized units, including one, two, and more polymerized units. This mixture of urethane molecules comprising a variant number of polymerized units allows simple mixing of the above components in the preparation of the fluorochemical composition. The preferred classes of urethane oligomers that may be present are represented by the following general formulas: RfZR2-0 (-CONH-Q (A) m-NHCO-OR30-) nCONH-Q (A) -NHCO-X'RXSÍ (Y) 3 RfZR-0 (-CONH-Q (A) m- NHCO-OR30-) nCONHR1SY (Y) 3 R4-O (-C0NH-Q (A) ra-NHCO-0R30-) nCONH-Q (A) -NHCO- X'RxSi (Y) 3 R4-O (-CONH -Q (A) ra -NHCO-OR30-) nCONHR1Si (Y) 3 wherein: RfZR2- is a residue of at least one of the fluorochemical monoalcohols; Rf is a perfluoroalkyl group having 3 to about 8 carbon atoms, or a perfluoroheteroalkyl group having 3 to about 50 carbon atoms; Z is a covalent bond, sulfonamido (~ S02NR-), or carboxamido (-CONR-) where R is hydrogen or alkyl; R1 is an alkylene, heteroalkylene, aralkylene, or heteroaralkylene group, - R2 is a divalent straight or branched chain alkylene, cycloalkylene, or heteroalkylene group of 1 to 14 carbon atoms (preferably, 1 to 8 carbon atoms, more preferably, 1 to 4 carbon atoms, more preferably, two carbon atoms, and preferably, R 2 is alkylene or heteroalkylene of 1 to 14 carbon atoms); Q is a multivalent organic group which is a residue of the polyfunctional isocyanate compound; R3 is a divalent organic group which is a residue of the polyol and can be optionally substituted with or contains (i) water solubilizing groups, (ii) perfluorinated groups or (III) silane groups; X 'is -O-, -S-, or -N (R) -, where R is hydrogen or alkyl; R4 is an optionally substituted long chain hydrocarbon derived from the long chain hydrocarbon monoalcohol; Each Y is independently a hydroxy; a hydrolyzable portion selected from the group consisting of alkoxy, acyloxy, heteroalkoxy, heteroacyloxy, halo, and oxime; or a non-hydrolyzable portion selected from the group consisting of phenyl, alicyclic, straight chain aliphatic, and branched chain aliphatic, wherein at least Y is a hydrolysable portion; A is a pendant group derived from a stabilizer or a water solubilizing group, provided that at least one A is a stabilizer; m is an integer from 0 to 2; and n, which is the number of polymerized units, is an integer from 2 to 10. The polyfunctional isocyanate groups that are useful in the present invention comprise radicals isocyanate bound to the multivalent organic group, Q, which may comprise a multivalent aliphatic, alicyclic or aromatic moiety; or a multivalent aliphatic, alicyclic or aromatic moiety linked to a biuret, an isocyanurate, or a uretdione, or mixtures thereof. The preferred polyfunctional isocyanate compounds contain two or three -NCO radicals. Compounds containing two -NCO radicals are comprised of aliphatic, alicyclic, araliphatic or aromatic divalent moieties to which the -NCO radicals are bound. Preferred compounds containing three -NCO radicals are comprised of monovalent isocyanatoaliphatic, isocyanatoalicyclic, or isocyanatoaromatic portions, which are attached to a biuret or an isocyanurate. Representative examples of suitable polyfunctional isocyanate compounds include isocyanate functional derivatives of the polyfunctional isocyanate compounds as defined herein. Examples of derivatives include, for example, those selected from the group consisting of ureas, biurets, allophanates, dimers and trimers (such as uretdiones and isocyanurates) of isocyanate compounds, and mixtures thereof. Any suitable organic polyisocyanate, such as an aliphatic, alicyclic, araliphatic or aromatic polyisocyanate, can be used either alone or in mixtures of two or more.

Polyfunctional aliphatic isocyanate compounds generally provide better light stability than aromatic compounds. Polyfunctional aromatic isocyanate compounds, on the other hand, are generally more economical and reactive towards polyols and other poly (active hydrogen) compounds which are polyfunctional aliphatic isocyanate compounds. Suitable aromatic polyfunctional isocyanate compounds include, for example, those selected from the group consisting of 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate, a TDI adduct with trimethylolpropane (available as DESMODUR ^ CB from Bayer Corporation, Pittsburgh, PA), TDI isocyanurate trimer (available as DESMODUR ™ IL from Bayer Corporation, Pittsburgh, PA), 4,4 '- diphenylmethane diisocyanate (MDl), 2,4' - diphenylmethane diisocyanate, 1,5-diisocyanato-naphthalene, 1 , 4-phenylene diisocyanate, 1,3-phenylene diisocyanate, l-methyoxy-2,4-phenylene diisocyanate, 1-chlorophenyl-2, -diisocyanate, and mixtures thereof. Examples of useful polyfunctional alicyclic isocyanate compounds include, for example, those selected from the group consisting of dicyclohexylmethane diisocyanate (H? 2MDI, commercially available as DES ODUR ™ 1, available from Bayer Corporation, Pittsburgh, PA), 4, '. -isopropyl-bis (cyclo-isocyanate), isophorone diisocyanate (IPDI), cyclobutan-1,3-diisocyanate, cyclohexan 1,3-diisocyanate, cyclohexane-1, -diisocyanate (CHDI), 1,4-cyclohexanbis (methylene isocyanate) (BDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), 3-isocyanatomethyl-3, 5, 5 -trimethylcyclohexyl isocyanate, and mixtures thereof. Examples of useful aliphatic polyfunctional isocyanate compounds include, for example, those selected from the group consisting of 1-tetramethylene diisocyanate, hexamethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (HDI), 1,12-dodecan diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate (TMDI), - 2,, 4-trimethyl-hexamethylene diisocyanate (TMDI), 2-methyl-1, 5-pentamethylene diisocyanate, diisocyanate dimer, urea of hexamethylene diisocyanate, biuret of hexamethylene 1,6-diisocyanate (HDI) (available as DESMODUR ™ N-100 and N-3200 from Bayer Corporation, Pittsburgh, PA), the HDI isocyanurate (available as DESMODUR1411 N-3300 and DESMODUR1 ^ N-3600 from Bayer Corporation, Pittsburgh, PA), a mixture of HDI isocyanurate and HDI uretdione (available as DESMODURM ™ N-3400 available from Bayer Corporation, Pittsburgh, PA), and mixtures thereof. Examples of useful araliphatic polyisocyanates include, for example, those selected from the group consisting of m-tetramethyl xylylene diisocyanate (m-TMXDI), p-tetramethyl xylylene diisocyanate (p-TMXDI), 1,4-xylylene diisocyanate (XDI), 1,3-xylylene diisocyanate, p- (1- isocyanatoethyl) -phenyl isocyanate, m- (3-isocyanatobutyl) -phenyl isocyanate, 4- (2-isocyanatocyclohexyl-methyl) -phenyl isocyanate, and mixtures thereof. Preferred polyisocyanates, in general, include those selected from the group consisting of hexamethylene 1,6-diisocyanate (HDI), 1,12-dodecan diisocyanate isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, MDl, all mentioned above, including DESMODURR N-100, N-3200, N-3300, N-3400,. N-3600, and mixtures thereof. Suitable commercially available polyfunctional isocyanates are exemplified by DESMODUR "11 N-3200, DESM0DURMR N-3300, DESMODUR1 ^ N-3400, DESMODUR ^ N-3600, DESMODURMR H (HDI), DESM0DURMR" W (bis [4-isocyanatocyclohexyl] methane) ), MONDURm M (4,4'-diisocyanatodiphenylmethane), MONDUR ™ 3, TDS (98% toluene 2,4-diisocyanate), MONDUR "11 TD-80 (a mixture of isomers of 80% 2,4 and 20% of 2,6-toluene diisocyanate), and DESMODUR ™ * N-100, each available from Bayer Corporation, Pittsburgh, Pa. Other useful triisocyanates are those obtained by reacting three moles of a diisocyanate with one mole of a triol. , toluene diisocyanate, 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate, or m-tetramethylxylene diisocyanate can be reacted with 1,1,1-tris (hydroxymethyl) propane to form triisocyanates.

The product of the reaction with m-tetramethylxylene diisocyanate is commercially available as CYTHANE "11 3160 (American Cyanamid, Stamford, Conn.) Suitable polyols for use in the preparation of additives of the present invention include those organic polyols having a functionality average hydroxyl of at least about 2 (preferably about 2 to 5, most preferably about 2 to 3, most preferably about 2, as diols are more preferred) The hydroxyl groups may be primary or secondary with primary hydroxyl groups which are preferred for their higher reactivity Mixtures of diols with polyols having an average hydroxyl functionality of about 2.5 to 5 (preferably about 3 to 4, more preferably about 3) It is preferred that such mixtures contain no more than about 20 weight percent of such polyole s, more preferably no more than about 10 percent, and more preferably no more than about 5 percent. Preferred mixtures are mixtures of diols and triols. Suitable polyols include those which comprise at least one aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aromatic, heteroaromatic or polymeric The polyols can be fluorinated polyols, such as perfluoropolyether diols. Preferred polyols are aliphatic or polymeric polyols containing hydroxyl groups as terminal groups or as groups that are pendant from the backbone chain of the polyol. The molecular weight (ie, the average molecular weight number) of polio is hydrocarbon generally can vary from about 60 to about 2000, preferably, from about 60 to about 1000, more preferably, from about 60 to about 500, in more preferably, from about 60 to about 300. The equivalent weight (ie, the average equivalent weight number) of hydrocarbon polyols can generally be in the range of about 30 to about 1000, preferably, about 30 to about 500, more preferably, about 30 to about 250. Polyols of higher equivalent weight may have a tendency to reduce the stain release properties provided by the chemical compositions of the present invention unless the polyol contains an Rf group or the polyol comprises a perfluoropolyether. If the polyol comprises a perf? Uoropolyether, it can have a molecular weight as high as about 7000 and can still provide suitable stain release properties. When the polyols of the present invention are diols, the diols can be substituted with or contain other groups. Accordingly, a preferred diol is selected from the group consisting of a branched-chain or straight hydrocarbon diol, a diol containing at least one water-solubilizing group, a fluorinated diol comprising a monovalent or perfluorinated divalent group. , a diol comprising a silane group, a polyalkylsiloxane diol, a polyarylsiloxane diol, and mixtures thereof Solubilization groups include carboxylate, sulfate, sulfonate, phosphate, phosphonate, ammonium, quaternary ammonium, and the like. perfluorinated monovalent groups (Rf) can be perfluoroalkyl and perfluoroheteroalkyl, and perfluorinated divalent groups can be perfluoroalkylene and perfluoroheteroalkylene. Perfluoroalkyl groups are preferred, with perfluoroalkyl groups having from 2 to 6 carbon atoms which are more preferred and perfluoroalkyl groups having 4 to 6 carbon atoms. carbon atoms that are more preferred Another embodiment comprises perfluoroheteroalkyl groups that They have 6 to 50 carbon atoms. The perfluorinated divalent groups are preferably perfluoroheteroalkylene groups. The perfluoroheteroalkylene groups are preferably perfluoropolyether groups having from about 3 to about 50 carbon atoms.

When the diol further comprises a silane group, the silane groups of the diol may contain one, two or three hydrolyzable groups on the silicon atom. Hydrolyzable groups are as defined below. Polyalkylsiloxane diols include, for example, hydroxyalkyl terminated polydimethyl siloxanes, and the like. The polyarylsiloxane diols are essentially the same as the polyalkylsiloxanes with some or all of the methyl groups replaced with phenyl groups, such as hydroxyalkyl-terminated polydiphenylsiloxane and hydroxyalkyl-terminated dimethyl-diphenyl siloxane copolymer. Representative examples of suitable non-polymeric polyols include alkylene glycols, polyhydroxyalkanes, and other polyhydroxy compounds. Alkylene glycols include, for example, 1,2-ethanediol; 1,2-propandiol; 3-chloro-1,2-propanediol; 1,3-propanediol; 1,3-butanediol; 1, -butandiol; 2-methyl-l, 3-propanediol; 2,2-dimethyl-1,3-propandiol (neopentyl glycol); 2-ethyl-l, 3-propanediol; 2, 2-diethyl-l, 3-propanediol; 1,5-pentanediol; 2-ethyl-1,3-pentanediol; 2, 2, 4-trimethyl-l, 3-pentanediol; 3-methyl-1,5-pentanediol; 1,2-hexanediol; 1,5-hexanediol; 1,6-hexanediol; 2-ethyl-l, 6-hexanediol; bis (hydroxymethyl) cydohexane; 1,8-octandiol; bicyclo-octandiol; 1, 10-decanediol; tricyclo-decanediol; norbornandiol; and 1,18-dihydroxyoctadecane. The polyhydroxyalkanes include, for example, glycerin, trimethylolethane; trimethylolpropane; 2-ethyl-2- (hydroxymethyl) -1,3-propanediol; 1/2, 6-hexantriol; pentaerythritol, quinitol; mannitol; and sorbitol. Other polyhydroxy compounds include, for example, di (ethylene glycol); tri (ethylene glycol); tetra (ethylene glycol); tetramethylene glycol; dipropylene glycol; diisopropylene glycol; tripropylene glycol; bis (hydroxymethyl) propionic acid; N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane; bicine, - N-bis (2-hydroxyethyl) Perfluorobutylsulfonamide; 1, 11- (3,6-dioxaundecan) diol; 1,14- (3, 6,9, 12-tetraoxatetradecan) diol; 1, 8- (3,6-dioxa-2, 5, 8-trimethyloctan) diol; 1, 14- (5, 10-dioxatetradecan) diole; Castor oil; 2-butyn-l, 4-diol; N, N-bis (hydroxyethyl) benzamide; 4,4'-bis (hydroxymethyl) diphenylsulphone; 1,4-benzenedimethanol; 1,3-bis (2-hydroxyethyoxy) benzene; 1,2-dihydroxybenzene; resorcinol; 1, -dihydroxybenzene; 3,5-dihydroxybenzoic acid; 2,6-dihydroxybenzoic acid; 2,5-dihydroxybenzoic acid; 2,4-dihydroxybenzoic acid; 1/6-dihydroxynaphthalene; 2,6-dihydroxynaphthalene; 2,5-dihydroxynaphthalene; 2,7,7-dihydroxynaphthalene; 2, 2'-biphenol; 4,4'-biphenol; 1,8-dihydroxybiphenyl; 2,4-dihydroxy-6-methyl-pyrimidine; 4,6-dihydroxypyrimidine; 3, 6-dihydroxypyridazine; bisphenol A; 4, 4'-ethylidenebisphenol; 4,4 '-isopropylidenebis (2,6-dimethylphenol); bis (4-hydroxyphenyl) methane; 1, l-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol C); l, 4-bis (2- hydroxyethyl) iperazine; bis (4-hydroxyphenyl) ether; as well as other aliphatic, heteroaliphatic, saturated alicyclic, aromatic, saturated heteroalicyclic, and heteroaromatic polyols; and the like, and mixtures thereof. Representative examples of useful polymeric polyols include polyoxyethylene, polyoxypropylene and polypropylene glycols and triols terminated in ethylene oxide of molecular weights from about 200 to about 2000, which correspond to equivalent weights of about 100 to about 1000 for the diols or about 70 to about 700 for triols; polytetramethylene glycols of varying molecular weight; polydialkylsiloxane diols of varying molecular weight; polyesters terminated in hydroxy and hydroxy-terminated polylactones (for example, polycaprolactone polyols); hydroxy-terminated polyalkadienes (for example, hydroxyl-terminated polybutadienes); and similar. Mixtures of polymeric polyols can be used if desired. Useful commercially available polymer polyols include poly (ethylene glycol) CARBOWAXm materials in the range of average molecular weight (Mn) from about 200 to about 2000 (available from Union Carbide Corp., Danbury, CT); ' materials of poly (propylene glycol) such as PPG-425 (available from Lyondell Chemical Company, Houston, TX); block copolymers of poly (ethylene glycol) and poly (propylene glycol) such as "PLLTRONIC1 ^ L31 (available from BASF Corporation, Mount Olive, NJ), ethoxylate of bisphenol A, propyl peroxylate of Bisphenol A, and propoxylate / Bisphenol A ethoxylate (available from Sigma-Aldrich, Milwaukee, Wl); polyethemethylene ether glycols such as POLYMEGMR 650 and 1000- (available from Quaker Oats Company, Chicago, IL) and TERATHANEMR polyols (available from EI duPont de Nemours, Wilmington, DE ); hydroxyl-terminated polybutadiene resins such as POLY BDMR materials (available from Elf A oeheñi Philadelphia, PA); the "PeP" series (available from Wyandotte Chemicals Corporation, Wyandotte, MI) of polyoxyalkylene tetroles having groups secondary hydroxyl, eg, "PeP" 450, 550, and 650; polycaprolactone polyols with Mn in the range of about 200 to about 2000 such as TONE ™ 1 0201, 0210, 0301, and 0310 (available from Union Carbide Corp. , Danbury, CT); "PARAPLEX1" 11 U-148"(available from Rohm and Hass Co., Philadelphia, PA), an aliphatic polyester diol, polyester polyols such as the poly (ethylenedipate) polyols MULTRON" 11 (available from Mobay Chemical Corp., Irvine, CA); polycarbonate diols such as DURACARB 120, a hexandiol carbonate with Mn = 900 (available from PPG Industries, Inc., Pittsburgh, PA); Y Similar; and mixtures thereof. Useful non-fluorinated polyols include 2,2-bis (hydroxymethyl) propionic acid; N, N-bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane; bicycle; 3,5-dihydroxybenzoic acid; 2,4-dihydroxybenzoic acid; 1, 2-ethanediol; 1,2- and 1,3-propandiol; 1,3-butanediol; 1, -butandiol; neopentyl glycol; 1,5-pentanediol; 3-methyl-1,5-pentanediol; 1,2-hexanediol; 1,5-hexanediol; 1,6-hexanediol; bis (hydroxymethyl) cydohexane; 1,8-octandiol; 1, 10-decanediol di (ethylene glycol); tri (ethylene glycol); tetra (ethylene glycol) di (propylene glycol); di (isopropylene glycol) tri (propylene glycol); poly (ethylene glycol) diols (average molecular weight number from about -200 to about 1500); poly (di (ethylene glycol) naphthalate) diol (having a number average molecular weight of, for example, about 350 or about 575); poly (propylene glycols) diols (average molecular weight number from about 200 to about 500); block copolymers of poly (ethylene glycol) and poly (propylene glycol) such as PLURONIC ^ L31 (available from BASF Corporation, Mount Olive, NJ); polydimethylsiloxane diol; polycaprolactone diols (average molecular weight number from about 200 to about 600); resorcinol; hydroquinone; 1,6-dihydroxynaphthalene; 2,5-dihydroxynaphthalene; 2,6- dihydroxynaphthalene; 2,7,7-dihydroxynaphthalene; 4,4'-biphenol; bisphenol A; bis (4-hydroxyphenyl) methane; and the like; and mixtures thereof. More preferred polyols include bis (hydroxymethyl) propionic acid; bicycle; N-bis (2-hydroxyethyl) perfluorobutylsulfonamide '; 1, 2-ethanediol; 1,2-propandiole; 1,3-propanediol; 1,4-butanediol; neopentyl glycol; 1,2-hexanediol; "-1,6-hexanediol; di (ethylene glycol); tri (ethylene glycol);" 1,4-bis (1-hydroxy-1,1-dihydroperfluoropropoxy) perfluoro-n-butane (HOCH2CF2CF20 (CF2) 4OCF2CF2CH2OH); fluorinated oxetane polyols made by the fluorinated oxetane ring opening polymerization such as POLY-S-FOX ^ (available from Omnova Solutions, Inc., Akron Ohio); poly (di (ethylene glycol) phthalate diol) (having a number average molecular weight of, for example, about 350 or about 575); poly (ethylene glycol) diols (having a number average molecular weight of, for example, about 200, 300, 400); diol of polydimethylsiloxane; polypropylene glycol (having an average molecular weight number of, for example, about 425); dimer diol; polycaprolactone diol (having a number average molecular weight of, for example, about 530); 3,5-dihydroxybenzene; bisphenol A; resorcinol; hydroquinone; and mixtures thereof.

The polyol can additionally be selected from fluorinated polyols. Representative examples of suitable fluorinated polyols include RfS02N (CH2CH2OH) 2 such as N-bis (2-hydroxyethyl) perfluorobutylsulfonamide; RfOC6H4S02N (CH2CH2OH) 2; RfS02N (R ') CH2CH (OH) CH2OH such as C6F? 3S02N (C3H7) CH2CH (OH) CH2OH; Rf CH2CON (CH2CH2OH) 2; Rf CON (CH 2 CH 2 OH) 2; CF3CF2 (OCF2CF2) 3OCF2CON (CH3) CH2CH (OH) CH2OH; RfOCH2CH (OH) CH2OH such as C4F9OCH2CH (OH) CH2OH; RfCH2CH2SC3HeOCH2CH (OH) CH2OH; lO Rf CH2CH2SC3H6CH (CH2OH) 2; Rf CH2CH2SCH2CH (OH) CH2OH; RfCH2CH2SCH (CH2OH) CH2CH2? H; RfH2CH2CH2SCH2CH (OH) CH2OH such as C5F ?? (CH2) 3SCH2CH (OH) CH2OH; RfCH2CH2CH2OCH2CH (OH) CH2OH such as CsFn (CH2) 3OCH2CH (OH) CH2OH; Rf CH2CH2CH2OC2H4OCH2CH (OH) CH20H RfCH2CH2 (CH3) OCH2CH (OH) CH2OH; Rf (CH2) 4SC3H6CH (CH2OH) CH20H Rf (CH2) 4SCH2CH (CH2OH) 2; Rf (CH2) 4SC3H6OCH2CH (OH) CH2OH RfCH2CH (C4H9) SCH2CH (OH) CH2OH; RfCH2OCH2CH (OH) CH2OH RfCH2CH (OH) CH2SCH2CH2OH; RfCH2CH (OH) CH2SCH2CH2OH RfCH2CH (OH) CH2OCH2CH2OH; RfCH2CH (OH) CH2OH Rf R "'SCH (R' '' OH) CH (R" OH) SR "Rf, (RfCH2CH2SCH2CH2SCH2) 2C (CH2OH) 2; ((CF3) 2CFO (CF2) 2 (CH2) 2SCH2) 2C (CH2OH) 2; (Rf R "'SCH 2) 2 C (CH 2 OH) 2; 1,4-bis (1-hydroxy-l, 1-dihydroperf luoroethoxyethoxy) perfluoro-n-butane (HOCH2CF2OC2F40 (CF2) 4OC2F4OCF2CH2OH); 1,4-bis (1-hydroxy-1,1-dihydroperf luoropropoxy) perfluoro-n-butane 25 (HOCH 2 CF 2 CF 20 (CF 2) 4 OCF 2 CF 2 CH 2 OH); fluorinated oxetane polyols made by fluorinated oxetane ring aperture polymerization such as Poly-3-Foxmr (available from Omnova Solutions, Inc., Akron Ohio); polyether alcohols prepared by ring opening addition polymerization of an epoxide substituted with fluorinated organic group with a compound containing at least two hydroxyl groups as described in U.S. Patent No. 4,508,916 (Newell et al); and perfluoropolyether diols such as Fomblin ™ ZDOL (HOCH2CF20 (CF20) 8_12 (CF2CF20) 8-? 2CF2CH2OH, available from Ausimont); wherein Rf is a perfluoroalkyl group having I to 12 carbon atoms, or a perfluoroheteroalkyl group having "3 to about 50 carbon atoms with all perfluorocarbon chains present having 6 or fewer carbon atoms, or mixtures thereof R 1 is alkyl of 1 to 4 carbon atoms, R "is straight or branched chain alkylene of 1 to 12 carbon atoms, alkylenethio-alkylene of 2 to 12 carbon atoms, alkylene-oxyalkylene of 2 to 12 carbon atoms. carbon, or alkylene iminoalkyl or from 2 to 12 carbon atoms, wherein the nitrogen atom contains as a third substituent hydrogen or alkyl of 1 to 6 carbon atoms, and R '' 'is a straight or branched chain alkylene of 1; to 12 carbon atoms or an alkylene-polyoxyalkylene of the formula CrH2r (OCsH2S) n where r is 1-12, s is 2-6, and t is 1-40.The preferred fluorinated polyols include N-bis (2- hydroxyethyl) perfluorobutylsulfonamide; fluorinated oxoethane polyols made by fluorinated oxetane ring aperture polymerization such as Poly-3-Fox "(available from Omnova Solutions, Inc., Akron Ohio); polyether alcohols prepared by ring opening addition polymerization of an epoxide substituted with fluorinated organic group with a compound containing at least two hydroxyl groups as described in U.S. Patent No. 4,508,916 (Newell et al); perfluoropolyether diols such as Fomblin ZDOL (H0CH2CF20 (CF20) 8_? 2 (CF2CF20) 8_? 2CF2CH2OH, available from Ausimont); 1,4-bis (1-hydroxy-1, 1-dihydroperfluoroethoxyethoxy) perfluoro-n-butane (HOCH2CF2? C2F40 (CF2) 4? C2F4OCF2CH2? H); and 1,4-bis (1-hydroxy-1,1-dihydroperfluoropropoxy) perfluoro-n-butane (HOCH2CF2CF20 (CF2) 4OCF2CF2CH2OH). More preferred polyols comprised of at least one fluoro-containing group include N-bis (2-hydroxyethyl) perfluorobutylsulfonamide; 1,4-bis (1-hydroxy-1,1-dihydroperfluoropropoxy) perfluoro-n-butane (HOCH2CF2CF20 (CF2) 4OCF2CF2CH2OH). Suitable fluorochemical monoalcohols for use in the preparation of additives of the present invention include those comprising at least one Rf group. The groups f may contain straight chain, branched chain, or cyclic fluorinated alkylene groups or any combination of them. The Rf groups may optionally contain one or more heteroatoms (eg, oxygen, sulfur and / or nitrogen) in the carbon-carbon chain to form a carbon-heteroatom-carbon chain (ie, a heteroalkylene group). Fully fluorinated groups are generally preferred, but hydrogen or chlorine atoms may also be present as substituents, as long as no more than one atom is present for every two carbon atoms. It is further preferred that any Rf group contains at least about 40% fluoro by weight, more preferably at least about 50% fluoro by weight. The terminal portion of the group is generally fully fluorinated, preferably containing at least three fluoro atoms (eg, CF30-, CF3CF2-, CF3CF2CF2-, (CF3) 2N-, (CF3) 2CF-, or SF5CF2-). Perfluorinated aliphatic groups (ie, those of the formula CnF2n +? -) where n is 2 to 6 inclusive are the preferred Rf groups, with n = 3 to 5 being most preferred and with n = 4 being most preferred. Useful fluoro-containing monoalcohols include compounds of the following formula: Rf-Z-R2-OH wherein: Rf is a perfluoroalkyl group or a group perfluoroheteroalkyl as defined above; Z is a connecting group selected from a covalent bond, a "sulfonamido group, a carboxamido group, a carboxyl group, or a sulfinyl group, and R2 is a straight chain or branched chain alkylene group, cycloalkylene, or divalent heteroalkylene group. 1 to 14 carbon atoms, 1 to 4 carbon atoms, more preferably 2 carbon atoms.) Representative examples of useful fluoro-containing monoalcohols include the following: CF3 (CF2) 3S02N (CH3) CH2CH2OH, CF3 (CF2) 3S02N (CH3) CH (CH3) CH2OH, CF3 (CF2) 3S02N (CH3) CH2CH (CH3) OH, CF3 (CF2) 3S02N (CH2CH3) CH2CH2OH, CF3 (CF2) 3S02N (CH3) CH2CH2SCH2CH2OH, CsF? 3S02N (CH3) (CH2) 4OH, CF3 (CF2) 7S02N (H) (CH2) 3 OH, C8F? 7S02N (CH3) CH2CH2OH, CF3 (CF2) 7S02N (CH3) (CH2) 4OH, .C8F? 7S02N (CH3) (CH2) nOH , CF3 (CF2) 7S02N (CH2CH3) CH2CH2OH, CF3 (CF2) 7S02N (C2H5) (CH2) sOH, CF3 (CF2) 7S02N (C2HS) (CH2) nOH, CF3 (CF2) 6S02N (C3H7) CH2OCH2CH2CH2OH, CF3 (CF2 ) 7S02N (CH2CH2CH3) CH2CH2OH, CF3 (CF2) 9S02N (CH2CH2CH3) CH2CH2OH, CF3 (CF2) 7S02N (C4H9) CH2CH2OH, CF3 (CF2) 7S02N (C4H9) (CH2) 4OH, 2- (N-methyl-2- (-perf luoro- (2, 6-diethylmorpholinyl)) perfluoroethylsulfonamido) ethanol, C3F7CONHCH2CH2OH, C7F? 5CON (CH3) CH2CH2OH, C7F? 5CON (C2H5) CH2CH2OH, - C8F? 7CON (C2H5) CH2CH2OH, C8F? 7CON (CH3) (CH2) nOH, C4F9CF (CF3) CON (H) CH2CH2OH C6F? 3CF (CF3) CON (H) CH2CH2OH C7F? SCF (CF3) CON (H) CH2CH2OH C2F50 (C2F40) 3CF2CONHC2H4OH, CF30 (CF (CF3) CF20)? -3SCF (CF3) CH2OH, C2F50 (CF (CF3) CF20)? -36CF (CF3) CH2OH, C3F70 (CF (CF3) CF20)? -36CF (CF3) CH2OH, C4F90 (CF (CF3) CF20)? _3eCF (CF3) CH2OH, C3F70 (CF (CF3) CF20) X2CF (CF3) CH2OH, CF30 (CF2CF2O)? -36CF2CH2OH, C2F50 (CF2CF20)? .3SCF2CH2OH, C3F70 (CF2CF20)? -36CF2CH2OH, C4F90 (CF2CF20)? _3SCF2CH2OH, n-C4F9OC2F4OCF2CH2OCH2CH2OH, CF30 ( CF2CF20) nCF2CH2OH, CF3CF (CF2C1) (CF2CF2) 6CF2CON (CH3) CH2CH2OH, CF3 (CF2) 6S02CH2CH2OH, CF3 (CF2) 7S02CH2CH2OH, CsF? COOCH2CH2OH, CF3 (CF2) 6COOCH2CH2OH, C6F? 3CF (CF3) COOCH2CH2CH (CH3) OH C8F? 7COOCH2CH2OH, C8F? 7 (CH2) uN (C2Hs) CH2CH2OH, C3F7CH2OH, CF3 (CF2) 5CH2OH, Perfluoro (cyclohexyl) methanol C4F9CH2CH2OH, CF3 (CF2) 5CH2CH2OH CF3 (CF2) 6CH2CH2CH2OH, CF3 (CF2) 7CH2CH2OH, CF3 (CF2) 7CH2CH2S02N (CH3) CH2CH2OH, CF3 (CF2) 5CH2CH2S02N (CH3) CH2CH2OH, CF3 (CF2) 3CH2CH2S02N (CH3) CH2CH2OH, CF3 (CF2) 7CH2CH2CH2OH, CF3CF (CF2H) (CF2) 10 (CH2) 2OH, CF3CF (CF2C1) (CF2)? Or (CH2) 2OH, Rf (CH2) 2S (CH2 ) 2 OH, C 4 F 9 (CH 2) 2 S (CH 2) 2 OH, R f (CH 2) 4 S (CH 2) 2 OH, f (CH 2) 2 S (CH 2) 3 OH, Rf (CH2) 2SCH (CH3) CH2OH, Rf (CH2) 4SCH (CH3) CH2OH, RfCH2CH (CH3) S (CH2) 20H, Rf (CH2) 2S (CH2) nOH, Rf (CH2) 2S (CH2) 30 ( CH2) 2OH, Rf (CH2) 30 (CH2) 2 OH, Rf (CH2) 3SCH (CH3) CH2OH, and the like, and mixtures thereof, wherein Rf is a perfluoroalkyl group of 2 to 16 carbon atoms. If desired, before using such alcohols, similar thiols can be used. Preferred fluoro-containing monoalcohols include 2- (N-methylperfluorobutanesulfonamido) ethanol, 2- (N-ethylperfluorobutanesulfonamido) ethanol, 2- (N-methylperfluorobutanesulfonamido) propanol, N-methyl-N-) 4-hydroxybutyl) perfluorohexansulfonamide, 1,1 , 2,2-tetrahydroperfluorooctanol, C4F9OC2F4OCF2CH2OCH2CH2OH, C3F7C0N (H) CH2CH2OH, C3F70 (CF (CF3) CF20)? -3eCF (CF3) CH20H, CF30 (CF2CF20)? -3SCF2CH2OH, and the like, and mixtures thereof. Silane compounds suitable for use in the chemical compositions of the present invention are those of the following formula: ## STR4 ## wherein X, Rx, and Y are as previously defined. By thus, these silane compounds contain one, two, or three hydrolysable groups (Y) in the silicon and an organic group that includes an isocyanate-reactive radical or active reactive hydrogen (X-R1). Any of the conventional hydrolysable groups, such as those selected from the group consisting of alkoxy, acyloxy, heteroalkoxy, heteroacyloxy, halo, oxime, and the like, can be used as the hydrolysable group (Y). The hydrolysable group (Y) is preferably alkoxy or acyloxy and more preferably alkoxy. When Y is halo, the hydrogen halide released from the halogen-containing silane can cause polymer degradation when cellulose substrates are used. When Y is an oxime group, lower oxime groups of the formula -N = CR 5 R 6, wherein R 5 and R 6 are monovalent lower alkyl groups comprising about 1 to about 12 carbon atoms, which may be the same or different, preferably selected of the group consisting of methyl, ethyl, propyl, and butyl, are preferred. Representative divalent bridging radicals (Rx) include, for example, those selected from the group consisting of -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2C6H4CH2CH2-, and -CH2CH20 (C2H40) 2CH2CH2N (CH3) CH2CH2CH2-. Other preferred silane compounds are thosewhich contain one or two hydrolysable groups, such as those having the structures R2OSi (R7) 2R1XH and (R80) 2Si (R7) RXH, wherein R1 is as previously defined, and R7 and R8 are selected from the group consisting of a phenyl group, an alicyclic group, or a straight or branched aliphatic group having from about 1 to about 12 carbon atoms. Preferably, R7 and R8 are a lower alkyl group comprising 1 to 4 carbon atoms. After the hydrolysis of some of these terminal silyl groups, the inter-reaction with a substrate surface comprising -SiOH groups or other metal hydroxide groups to form siloxane or metal-oxano bonds, for example, + ROH it can happen The bonds thus formed, particularly Si-O-Si bonds, are water resistant and can provide improved durability of the stain release properties imparted by the chemical compositions of the present invention. Such silane compounds are well known in the art and many are commercially available or are readily prepared. Representative isocyanate-isocyanate-reactive silane compounds include, For example: H2NCH2CH2CH2Si (OC2H5) 3, H2NCH2CH2CH2SÍ (OCH3) 3, H2NCH2CH2CH2SÍ (0-N = C (CH3) (C2H5)) 3 HSCH2CH2CH2SÍ (OCH3) 3, HO (C2H4Ó) 3C2H4N (CH3) (CH2) 3Si (OC4H9 ) 3, H2NCH2C6H4CH2CH2SÍ (OCH3) 3, HSCH2CH2CH2Si (OCOCH3) 3, HN (CH3) CH2CH2SÍ (OCH3) 3, "HSCH2CH2CH2SiCH3 (OCH3) 2, (H3CO) 3SiCH2CH2CH2NHCH2CH2CH2SÍ (OCH3) 3, HN (CH3) C3HeSÍ (OCH3) 3 , CH3CH2OOCCH2CH (COOCH2CH3) HNC3H6Si (OCH2CH3) 3, CeH5NHC3HeSi (OCH3) 3, H2NC3H6SiCH3 (OCH2CH3) 2, HOCH (CH3) CH2OCONHC3H6SÍ (OCH2CH3) 3, (HOCH2CH2) 2NCH2CH2CH2SÍ (OCH2CH3) 3, and mixtures thereof. Representative of hydroxy-reactive silane compounds include, for example, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, and the like An exemplary fluorochemical urethane which can be used in the additives of the present invention is a waterborne dispersion comprising: • * HN (G; H-XCH-CH-) GJH + Higher Oligomers Optionally the additives of the present invention can additionally comprise stabilizers including, for example, ultraviolet (UV) absorbers and hindered amine light stabilizers comprising isocyanate-reactive groups that enable covalent incorporation into the polyurethane. Such reactable stabilizers may comprise, for example, one or more isocyanate-reactive groups such as amine, hydroxyl groups or the like. Preferably, the reactable stabilizers comprise hydroxyl groups. Some examples of UV absorbers that are suitable for use in the present invention protect the composition by absorbing radiation in the range of about 270-500 nanometers and releasing the energy in the environment through non-destructive means. Suitable UV absorbers include, for example, esters of isocyanate-reactant cinnamate, hydroxybenzophenones, benzotriazoles, substituted acrylates, salicylates, oxanilides, hydroxyphenyltriazines, and the like.

Representative examples of suitable reactable UV absorbers include 2-amino-5- Chlorobenzofenone, Tinuvín M1"R" R- 600 Tmuvín M 'R 400-2 Tinuvin ™ 1 405 TinuvinMK 1130 50% 38% H (OCH2CH2) S-7? H, 12%. Preferred UV absorbers include, for example, Tinuvin ™ 1405 and Tinuvin ™ 1130. The hindered amine light stabilizers (HALS) work by inhibiting the degradation of the alginate cement slurry coatings, which has already formed free radicals. An example of a suitable HALS is CGL-052 Antioxidants and thermal stabilizers may optionally be included in additives of the invention. Antioxidants and thermal stabilizers can help minimize the degrading effects of thermal degradation processes, photoinduced, and auto-catalytic. Suitable antioxidants and / or thermal stabilizers include, for example, sterically hindered phenols, bisphenols, aminophenols, secondary aromatic amines, hydroxybenzyl compounds, alkyl and aryl thioethers, thiobisphenols, phosphates and phosphonites, zinc thiocarbamates, benzofuranone lactone-based antioxidants, chillers of nickel, metal deactivators or complexing agents, and the like. The additives of the invention optionally may contain water solubilizing compounds (W-Rx-X) comprising one or more water solubilization groups and at least one isocyanate-reactive group. These water solubilizing compounds include, for example, diols and monoalcohols comprising one or more water solubilization groups, aggregated in addition to the one or more polyols and one or more monoalcohols as described above. Solubilization groups of water solubilization compounds include, for example, carboxylate, sulfate, sulfonate, phosphate, phosphonate, ammonium and quaternary ammonium groups. Such groups can be represented as -C02M, -OS03M, -S03M, -OP03M, -PO (OM) 2, -NR2HX, -NR3X, -NRH2X, and -NH3X, respectively, wherein M is H or an equivalent of a monovalent or divalent soluble cation such as sodium, potassium, calcium, and NR3H +; X is a soluble anion such as those selected from the group consisting of halide, hydroxide, carboxylate, sulfonates, and the like; and R is selected from the group consisting of a phenyl group, a cycloaliphatic group, or a straight or branched aliphatic group having from about 1 to about 12 carbon atoms. Preferably, R is a lower alkyl group having from 1 to 4 carbon atoms. The group -NR3X is a salt of a water soluble acid, for example trimethyl ammonium chloride, pyridinium sulfate, etc. or an ammonium substituent. The group -NR2HX is the salt of a water soluble acid, such as propionate or dimethyl ammonium acetate. The -NRH2X group is the salt of a water soluble acid, such as propionate or methyl ammonium acetate. The -NH3X group is the salt of a water-soluble acid, such as propionate or ammonium acetate. The salt form can be made by simple, neutralization of the acid group with a base such as an amine, a quaternary ammonium hydroxide, an alkali metal hydroxide or carbonate, or the like; or alternatively by simple reaction of the amino group with a carboxylic acid, a sulfonic acid, an acid halo, or the like. The carboxylic acid groups in salt form are preferred because they have been found to impart water solubility to the chemical compositions of the present invention without causing undue loss of the durable spotting release properties imparted by the chemical composition. The group containing hydrogen that reacts with isocyanate is selected from the group consisting of -OH, -SH, NH2, and NRH wherein R is selected from the group consisting of a phenyl group, a cycloaliphatic group, or a straight or aliphatic group branched having from about 1 to about 12 carbon atoms. Preferably, R is a lower alkyl group having from 1 to 4 carbon atoms. A suitable representative diol with a solubilization group is 2,2-bis (hydroxymethyl) propionic acid and its salts such as its ammonium salt. A suitable representative monoalcohol with a solubilization group is glycolic acid (HOCH2COOH) and its salts. The amount of solubilization group in water should be sufficient to solubilize the chemical composition Typically, the isocyanate: solubilization group ratio should be from about 3: 1 to about 16: 1, preferably from about 5: 1 to about 11: 1. Illustrative water solubilization compounds having suitable water solubilizing groups include, but are not limited to, those independently selected from the group consisting of HOCH 2 COOH; HSCH2COOH; (HOCH2CH2) 2NCH2COOH; HOC (C02H) (CH2C02H) 2; (H2N (CH2) nCH2) 2NCH3 wherein n is an integer from 1 to 3; (H0CH2) 2C (CH3) CO0H; (HO (CH2) nCH2) 2NCH3 where n is an integer of 1 a. 3; HOCH2CH (OH) C02Na; N- (2-hydroxyethyl) iminodiacetic acid (HOCH2CH2N (CH2COOH) 2); L-glutamic acid (H2NCH (COOH) (CH2CH2COOH)); aspartic acid (H2NCH (COOH) (CH2COOH)); glycine (H2NCH2COOH); 1,3-diamino-2-propanol-N, N, N ', N' -tetraacetic acid (HOCH (CH2N (CH2COOH) 2) 2); iminodiacetic acid (HN (CH2C00H) 2); mercaptosuccinic acid (HSCH (COOH) (CH2COOH)); H2N (CH2) 4CH (COOH) N (CH2COOH) 2; HOCH (COOH) CH (COOH) CH2COOH; (HOCH2) 2CHCH2COO) "(NH (CH3) 3) +; CH3 (CH2) 2CH (OH) CH (OH) (CH2) 3C02K; H2NCH2CH2OS03Na; H2NC2H4NHC2H4S03H; H2NC3HeNH (CH3) C3H6S03H; (HOC2H4) 2NC3HsOS03Na; (HOCH2CH2) 2NCeH4OCH2CH2OS02OH; N-methyl-4 - (2,3-dihydroxypropoxy) pyridinium chloride, ((H2N) 2C6H3S03) ~ (NH (C2H5) 3) +; dihydroxybenzoic acid; 3, 4-dihydroxybenzyl acid; 3 - (3,5-dihydroxy-enyl) propionic acid; salts of the amines, carboxylic acids, and sulfonic acids above; and mixtures thereof. The additives of the present invention can be made according to the following stepped synthesis. As one skilled in the art could understand, the order of the steps is not limiting and can be modified to produce a desired chemical composition. In the synthesis, the polyfunctional isocyanate compound, the reactable stabilizers, and the polyol are dissolved together under dry conditions, preferably in a solvent, and then the resulting solution is heated to about 40 to 80 ° C (preferably, about 60 to 70 ° C). C) with mixing in the presence of a catalyst for a mean to two hours, preferably one hour: Depending on the reaction conditions (e.g., reaction temperature and / or polyfunctional isocyanate used), a catalyst level of up to about 0.5 percent in weight. of the polyfunctional isocyanate / polyol / stabilizer mixture can be used, but typically about 0.00005 to about 0.5 percent by weight is required, 0.02 to 0.1 percent by weight is preferred. Suitable catalysts include, but are not limited to, tertiary amine and tin compounds. Examples of useful tin compounds include tin II and tin IV salts such as stannous octoate, dilaurate of dibutyltin, dibutyltin diacetate, dibutyltin di-2-ethylhexanoate, and dibutyltin oxide. Examples of useful tertiary amine compounds include triethylamine, tributylamine, triethylenediamine, tripropylamine, bis (dimethylaminoethyl) ether, morpholine compounds such as ethyl morpholine, and 2,2 '-dimorpholinodiethyl ether, 1,4-diazabicyclo [2.2.2] octane (DABCO, Sigma-Aldrich Chemical Co., Milwaukee, Wl), and 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU, Sigma-Aldrich Chemical Co., Milwaukee, Wl). Tin compounds are preferred. A mixture of polyols can be used in place of a single polyol. For example, in a preferred embodiment a polyol mixture comprising a polyol with a solubilization group in water and a polyol with a group Rf is used. When the polyfunctional isocyanate compound is a triisocyanate, the polyol is preferably a diol to prevent undesired gelation, which can occur when polyols having three or more hydroxyl groups are reacted with a triisocyanate. The resulting functional isocyanate urethane compounds and oligomers are then further reacted with one or more of the monoalcohols described above, in conjunction with the reactive stabilizers, if desired. The monoalcohols are added to the above reaction mixture, and react with a portion of the remaining NCO groups. The above temperatures, dry conditions, and mixing are continued an average to two hours (preferably, one hour). The stabilizer and hydrocarbon groups containing fluoro-terminal and / or long-chain are thus linked to the isocyanate-functional urethane compounds and oligomers. These compounds and oligomers are further functionalized with the silane groups described above by reacting a portion or all of the remaining NCO groups in the resulting mixture with one or more of the isocyanate-reactive silane-reagent compounds described above. Accordingly, the silane compounds are added to the reaction mixture, using the same conditions as with the previous additions. Aminosilanes are preferred, due to the rapid and complete reaction that occurs between the -NCO groups and the amino groups of the silane compound. Functional isocyanate silane compounds can be used and are preferred when the ratio of polyfunctional isocyanate compound to polyol and monoalcohol is such that the resulting oligomer has a terminal hydroxyl group. The water solubilization compounds can be added and reacted with all or a portion of the -NCO groups under the conditions described above in any of the steps described above. By example, as mentioned above, the water solubilization compound can be added as a mixture with the polyol. Alternatively, the water solubilization compound can be added after the reaction of the polyol with the polyfunctional isocyanate, as a mixture with the monoalcohols, after the reaction of the polyol and monoalcohol with the polyfunctional isocyanate, as a mixture with the silane, or after the reaction of the polyol, monoalcohol and silane with the polyfunctional isocyanate When the water solubilizing compound is u? monoalcohol, it is preferably added as a mixture with the monoalcohol containing fluoro or the long chain hydrocarbon monoalcohol. the water solubilizing compound is a diol, it is preferably added as a mixture with the polyol When the chemical composition of the present invention contains a urethane oligomer having one or more carboxylic acid groups, the solubility of the composition in water can It is further increased by forming a salt of the carboxylic acid groups. basic salt forming sites, such as tertiary amines, quaternary ammonium hydroxides, and inorganic bases, including, for example, those selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, hydroxide, Calcium, magnesium hydroxide, zinc hydroxide, and barium hydroxide, may be used in a sufficient amount (ie, in an amount to maintain a pH of more than about 6). These basic salt-forming compounds can preferably be added in the aqueous phase, but optionally in the preparation of the urethane oligomers, to form the salts with the incorporated, pendant and / or terminal carboxylic acid groups in the urethane oligomer. Examples of useful amine salt-forming compounds include, for example, those selected from the group consisting of ammonia, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triethanolamine, diethanolamine, methyldiethanolamine, morpholine, N-methylmorpholine, dimethylethanolamine, and mixtures thereof. Preferred salt-forming compounds include, for example, those selected from the group consisting of ammonia, trimethylamine, dimethylethanolamine, methyldiethanolamine, triethylamine, tripropylamine, and triisopropylamine, since the chemical compositions prepared therefrom are not excessively hydrophilic in coating and curing. . Because certain salts formed by the reaction of salt-forming compounds, such as hydroxide potassium in combination with a carboxylic acid group, may result in undesired reaction with NCO groups, it is preferred to add the salt-forming compound in an aqueous phase after all the diols, alcohol and silane compounds have been reacted with the NCO groups of the compound polyfunctional isocyanate. The molar ratios of the additive components of the present invention are approximately as follows: one or more polyfunctional isocyanate compounds and one or more polyols are used in a molar ratio of from about 1: 0.25 to about 1: 0.45; one or more polyfunctional isocyanate compounds and one or more monoalcohols are used in a molar ratio of from about 1: 0.30 to about 1: 0.60; one or more polyfunctional isocyanate compounds and one or more silanes are used in a molar ratio of from about 1: 0.001 to about 1: 0.15; one or more polyfunctional isocyanate compounds and one or more stabilizers are used in a molar ratio of from about 1: 0.001 to about 1: 0.1; and one or more polyfunctional isocyanate compounds and one or more water solubilization compounds are used in a molar ratio of from about 1: 0 to about 1: 1.6.

The molar ratios of the additive components of the present invention are preferably as follows: one or more polyfunctional isocyanate compounds and one or more polyols are used in a molar ratio of from about 1: 0.35 to about 1: 0.42.; one or more polyfunctional isocyanate compounds and one or more monoalcohols are used in a molar ratio of from about 1: 0.45 to about 1: 0.55; one or more polyfunctional isocyanate compounds and one or more silanes are used in a molar ratio of from about 1: 0.03 to about 1: 0.08; one or more polyfunctional isocyanate compounds and one or more stabilizers are used in a molar ratio of from about 1: 0.01 to about 1: 0.05; and one or more polyfunctional isocyanate compounds and one or more water solubilization compounds are used in a molar ratio of from about 1: 0 to about 1: 1.0.

Other Ingredients Polymeric cement slurries contain a polymeric resin and filler material. Illustrative examples include epoxy-containing resins and acrylate-containing resins. Illustrative examples of fillers include siliceous sand particles, stone limestone, titanium dioxide, talc, and the like. Illustrative examples of polymeric cement slurries are described in - "U.S. Patent Nos. 4,616,050, 4,472,540, and 3,859,233.

Mixing The cement grout compositions of the invention can be made easily by mixing additives as described herein with the other polymeric grout component materials by any suitable means. The polymeric cement slurry compositions of the invention typically contain from about 0.01 to about 1 weight percent of the additive based on a dry base. The cement slurry compositions of the invention may optionally comprise biocides (e.g., mildicides) to inhibit the growth of biological material such as algae, mildew, and molds on coated substrates. A preferred biocide, for example, is zinc pyridenthione. Additionally, it may be desirable to add surfactants, anti-foam agents, anti-slip particles, and / or colorants (e.g., stains, or pigments).

Applications The cement grout compositions of the invention can be used in any of a variety of interior and exterior applications with a variety of tile materials, for example, ceramic pieces, stone, etc. for a variety of applications including floor covering, pool covers, walls, shower surroundings, etc. It is noted that in relation to this date, the best method known to the applicant to carry out said invention, it is what is clear from the present description of the invention.

Claims (1)

CLAIMS Having described the invention as above, the contents of the following claims are claimed as property:

1. Composition of polymeric cement slurry, characterized in that it comprises one or more urethane polymers of at least two polymerized units, wherein the oligomers comprise the reaction product of: (a) one or more polyfunctional isocyanate compounds, (b) one or more polyols, (c) one or more monoalcohols selected from the group consisting of fluorocarbon monoalcohols, optionally substituted long chain hydrocarbon monoalcohols, and mixtures thereof; and (d) one or more silanes of the following formula: X-Rx - Si - (Y) 3 wherein X is a reactive isocyanate group selected from -NH2, -SH, -OH, or -NRH, where R is selected of the group consisting of phenyl groups, straight and brad aliphatic, alicyclic, and aliphatic ester, Rx is an alkylene, heteroalkylene, aralkylene, or heteroalkylene group, and each Y is independently a hydroxyl, a hydrolyzable portion selected from the group consisting of alkoxy, acyloxy, heteroalkyloxy, heteroacyloxy, halo, and oxime, or a non-hydrolyzable portion selected from the group consisting of phenyl, "alicyclic, straight-chain aliphatic, and brad chain aliphatic, wherein at least one Y is a hydrolysable portion.