SILICONATES WITH FLUORINATED ALKYLSILANES AND AMINOSILANES, AND SURFACE-TREATMENT METHODS USING

THE COMPOSITIONS

TECHNICAL FIELD

[0001] The present invention relates in general to water-dispersible surface-treatment compositions and, more particularly, to water-dispersible surface-treatment compositions comprising at least one silicone compound.

BACKGROUND

[0002] It is known that a limited number of alkali-metal alkyl siliconates can be prepared as aqueous compositions, typically by reacting chlorosilanes or alkoxysilanes with an aqueous alkali-metal hydroxide. For example, potassium methyl siliconate may be prepared by reacting MeSi(OMe)3 with KOH in water, followed by removal of methanol. This reaction effectively resembles dissolving the methyltrimethoxysilane in the aqueous potassium hydroxide. Even so, this dissolution-type chemistry is not effective when the starting materials contain fluoroalkyl groups or alkyl groups with greater than three carbon atoms.

[0003] Potassium methyl siliconate is commercially available as an aqueous solution containing approximately 40% (w/w) of the siliconate. The commercially available potassium methyl siliconate may be diluted by the end user, typically to about 3% (w/w), and then may be applied to substrates such as masonry, brick, gypsum, or paper. Over time, the potassium methyl siliconate reacts with atmospheric C0 ₂ to form an alkali-metal carbonate and a silsesquioxane resin. The silsesquioxane resin renders the treated surfaces of the substrates hydrophobic.

[0004] For organosiliconate surface-treatment agents to render a surface hydrophobic, it may be desirable for the silsesquioxane resin formed after reaction of the siliconate with atmospheric C0 ₂ to comprise hydrophobic groups such as long alkyl chains or fluoroalkyl groups. Fluoroalkyl groups are particularly desirable in surface-treatment agents because they may render surfaces impervious to both water and oils. Desirable compounds in this regard may include, for example, butyl siliconates, hexyl siliconates, phenyl siliconates, tolyl siliconates, octyl siliconates, dodecyl siliconates, and fluoroalkyl siliconates. Yet, none of these compounds having the hydrophobic groups can be formed as aqueous solutions in the same manner as potassium methyl siliconate, i.e., by simply dissolving a silane in potassium hydroxide, or by any other known route.

[0005] Thus, there remains a need for methods to form water-dispersible compositions containing alkali metal organosiliconates having hydrophobic groups, especially groups with more than three carbon atoms or with fluoroalkyl functionalities.

SUMMARY

[0006] According to embodiments disclosed herein, water-soluble or water-dispersible aqueous compositions are provided. The aqueous compositions comprise an alkali-metal Ci- C ₄ hydrocarbyl siliconate, at least one aminosilicon compound, and at least one organosilicon compound having fluoroalkyl groups, organic groups with more than 3 carbon atoms, or both. Methods for preparation and use of the compositions are disclosed.

[0007] Embodiments disclosed herein are directed to water-dispersible aqueous compositions comprising (I) a solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate, (II) a solvated organosilicon component derived from an organosilicon compound, and (III) a solvated aminosilicon component derived from an aminosilane. The solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate may be a hydrocarbyl siliconate salt, as defined herein, charge- balanced by any alkali metal cation. The organosilicon compound is at least one silane having a formula R 3 _x SiZ 1 ₄ - _x , where each Z1 is selected from the group consisting of -OR 2 ,

2 3

-Cl, and -OH; each R is a Ci-C ₄ hydrocarbyl; each R is selected from the group consisting of Ci-Cs hydrocarbyl, C3-C ₈ fluorohydrocarbyl, phenyl, tolyl, and R ⁴ , such that at least one group R in the organosilicon compound is C ₄ -Cs hydrocarbyl, C3-C ₈ fluorohydrocarbyl or R ⁴ ; R ⁴ is -R ⁵ -0-(CH ₂ )r _f -R ⁶ , where <i is 1 or 2; R ⁵ is a C3 linear alkylene or a C ₄ -C ₅ branched alkylene; R ⁶ is a Ci-C ₆ perfluoroalkyl; and x is 1, 2, or 3. The aminosilane is at least one compound having the formula R ^A R ⁹ _y SiZ ² ₃ - _y , where each Z ² is selected from the group consisting of -OR ⁷ and -OH; each R ⁷ is a Ci-C ₄ hydrocarbyl; each R ^A is bonded to the

8 10 8 10 8 silicon atom and is a group (-R -NR ) _m -R -NR ₂ , where m is from 0 to 4; each R is independently a C ₂ -C ₄ hydrocarbylene; each R ⁹ is a Ci-C ₃ hydrocarbyl; each R ¹⁰ is independently selected from the group consisting of-H and Ci-C ₃ hydrocarbyl; and y is 0, 1 or 2.

[0008] Further embodiments disclosed herein are directed to methods for the forming water-dispersible aqueous compositions. The methods for forming the water-dispersible aqueous compositions may comprise adding an organosilicon compound and an aminosilane to an aqueous solution containing a solvated alkali -metal C ₁ -C ₄ hydrocarbyl siliconate to form a reaction mixture. The reaction mixture then may be heated, manipulated, or both, to completely solvate the organosilicon compound in the reaction mixture.

[0009] Still further embodiments disclosed herein are directed to methods for treating a substrate surface of a substrate with at least one water-dispersible aqueous composition. The methods may comprise applying a coating of a water-dispersible aqueous composition, according to one or more embodiments disclosed herein, having a total-solids content of from 0.1 wt.% to 45 wt.% such as, for example, from 0.1 wt.% to 10 wt.%. The coating then is exposed to atmospheric carbon dioxide, such that a cured, hydrophobic, waterproof, and optionally oil-proof layer forms within the treated substrate through a reaction of the water- dispersible aqueous composition with the atmospheric carbon dioxide.

[0010] These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.

DETAILED DESCRIPTION

[0011] Features and advantages of the invention will now be described with occasional reference to specific embodiments. However, the invention may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of the invention to those skilled in the art.

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting. As used in the specification and appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0013] As used in the specification and appended claims, the terms "each X is A, B, or C" and "each X is selected from the group consisting of A, B, and C" are equivalent to the phrase "each X is independently selected from the group consisting of A, B, and C." All of these terms are intended to mean that a plurality of groups X on the same molecule, on a plurality of molecules within a composition, or both, as the context would indicate, can be all the same as each other, can be all different from one another, or can comprise any

conceivable mixture of A, B, and C, unless the context clearly indicates that any of these options are excluded. [0014] As used in the specification and appended claims, the term "each X is a Y," where Y represents a class having more than one member, is equivalent to the phrase "each X is independently selected from the group consisting of all members of the class Y," unless the context clearly indicates otherwise.

[0015] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth as used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless otherwise indicated, the numerical properties set forth in the specification and claims are approximations that may vary depending on the desired properties sought to be obtained in embodiments of the present invention. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. One of ordinary skill in the art will understand that any numerical values inherently contain certain errors attributable to the measurement techniques used to ascertain the values.

[0016] As used herein, the term "hydrocarbyl" refers to a monovalent radical formed by removing any one hydrogen from a hydrocarbon molecule, where a "hydrocarbon molecule" is any molecule consisting of hydrogen atoms and carbon atoms. Except where defined otherwise, the term "hydrocarbyl" encompasses linear groups, branched groups, cyclic groups, and combinations thereof, wherein any two neighboring carbon atoms may be joined by a single bond, a double bond, or a triple bond. As used herein, the term "C _x to C _y hydrocarbyl," where x and y are integers, refers to a hydrocarbyl having from x to y total carbon atoms and a sufficient number of hydrogen atoms to maintain the monovalency of the hydrocarbyl.

[0017] As used herein, the term "halohydrocarbyl" refers to a monovalent radical formed by removing any one hydrogen from a halohydrocarbon molecule. A "halohydro carbon molecule" is a molecule that results from replacing one or more hydrogen atoms of a hydrocarbon molecule with an equal number of halogen atoms. Unless otherwise noted, each halogen atom is independently selected from the group consisting of fluorine, chlorine, bromine, and iodine. Subsets of halohydrocarbyls include, for example,

"fluorohydrocarbyls" consisting of hydrogen atoms, carbon atoms, and fluorine atoms;

"chlorohydrocarbyls" consisting of hydrogen atoms, carbon atoms, and chlorine atoms; and "chloro fluorohydrocarbyls" consisting of hydrogen atoms, carbon atoms, chlorine atoms, and fluorine atoms. [0018] As used herein, the term "hydrocarbylene" refers to a divalent radical formed by removing any two hydrogen atoms from a hydrocarbon. The two hydrogen atoms may have been removed from the same carbon atom or from two different carbon atoms. The term "hydrocarbylene" encompasses linear groups, branched groups, cyclic groups, and combinations thereof, wherein neighboring carbon atoms may be joined by a single bond, a double bond, or a triple bond. Thus, "hydrocarbylene" encompasses both saturated hydrocarbylenes and unsaturated hydrocarbylenes. As used herein, the term "C _x to C _y hydrocarbylene," where x and y are integers, refers to a hydrocarbylene having from x to y total carbon atoms and a sufficient number of hydrogen atoms to maintain the divalency of the hydrocarbylene.

[0019] Alkali-metal organosiliconates are compounds containing an organosiliconate anion charge-balanced by one or more cations of an alkali metal such as lithium, sodium, potassium, rubidium, or cesium. As used herein, the term "organosiliconate" shall be construed according to the broadest definition understood by persons of ordinary skill in the relevant art and shall not be limited by any theory as to any precise structure of the anion inferred by characterization methods such as NMR.

[0020] Generally, the precise structure of siliconate anions in aqueous solution may be complex. In a simplified form siliconate anions may be represented by the general formula RSi(OH) _a (0 where R is a monovalent organic group and a + b = 3. The general formula encompasses monomeric species such as RSi(OH)2(CT) and RSi(OH)(CT)2; and also oligomeric species such as, for example, R(OH)(0 )Si-0-Si(OH)(0 )R,

R(OH)(0 )Si-0-Si(0 ) ₂ R, R(OH) ₂ Si-0-Si(OH)(0 )R,

R(OH)(0 )Si-0-Si(OH)R-0-Si(OH)(0 )R, R(OH) ₂ Si-0-Si(0 )R-0-Si(OH)(0 )R, and analogous larger species, each species having a statistical distribution of OH groups and CT groups.

[0021] In an alkali-metal organosiliconate in solution, each group O of each

organosiliconate anionic species is charge-balanced by one or more alkali-metal cations M ⁺ , (each M ⁺ = Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , or Cs ⁺ ). Typically, the ratio Si:M ⁺ of silicon atoms (Si) to alkali-metal cations (M ⁺ ) in an aqueous solution of an alkali-metal organosiliconate is greater than 1 or, alternatively, may range from about 0.8: 1 to about 1 : 1.5. For example, potassium methyl siliconate may have Si:M ⁺ of about 1 : 1.2. Sodium methyl siliconate may have Si:M ⁺ of about 1 : 1.1.

[0022] As used herein, the term "alkali-metal alkyl siliconate" refers to compounds or aqueous solutions in which siliconate anions of the above general formula and description are charge -balanced by alkali-metal cations selected from Li , Na , K , Rb , Cs , and mixtures thereof, where R is an alkyl group. Likewise, the term "alkali-metal hydrocarbyl siliconate" shall refer to alkali-metal alkyl siliconates, in which R is a hydrocarbyl group, as defined above.

[0023] As used herein, the term "alkali-metal C ₁ -C ₄ hydrocarbyl siliconate" shall refer to alkali-metal alkyl siliconates, in which R is a C ₁ -C ₄ hydrocarbyl group. Non- limiting examples of C ₁ -C ₄ hydrocarbyl groups include methyl, ethyl, /? -propyl, 1-methylethyl (isopropyl), n-butyl, 1-methylpropyl (isobutyl), 2-methylpropyl (sec-butyl), and

1,1-dimethylethyl (fert-butyl). In preferred embodiments, the C ₁ -C ₄ hydrocarbyl is methyl or ethyl.

[0024] A water-dispersible aqueous composition according to various non-limiting embodiments comprises (I) a solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate; (II) a solvated organosilicon component; and (III) a solvated aminosilicon component. As used herein, the term "solvated" means that the alkali-metal C ₁ -C ₄ hydrocarbyl siliconate, the organosilicon component, and the aminosilicon component are substantially solvated, preferably completely solvated, in the water-dispersible aqueous composition. As used herein, a component is "substantially solvated" when the component causes the water- dispersible composition to have a hazy appearance but does not form any visibly apparent agglomerates or precipitates within the water-dispersible aqueous composition. In this sense, a component is "completely solvated" when no solid form of the component is visibly detectable within the water-dispersible composition. Preferably, all components of the water- dispersible aqueous composition are completely solvated, such that the water-dispersible composition is a clear solution. As used herein, the term "water-dispersible" means that the composition may be diluted with an aqueous solvent, preferably water, more preferably deionized water, without resulting in precipitation of the solvated organosilicon component.

[0025] The solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I) is as defined above. The solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I) may be prepared by any known method or may be derived from any commercially available aqueous solution having an alkali-metal C ₁ -C ₄ hydrocarbyl siliconate component. The organosilicon component (II) is

3 1

derived from at least one organosilane of the formula R _x SiZ ₄ _ _x , defined below in detail. The solvated organosilicon component (II) may be formed, for example, by adding a liquid or solid organosilicon compound, described in detail below, to an aqueous solution containing the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I) and the aminosilicon component (III). The solvated aminosilicon component (III) is derived from at least one aminosilane of the formula R ^A R ⁹ R ¹⁰ _y SiZ ² ₃ -y, defined below in detail. The solvated aminosilicon component (III) may be formed, for example, by adding a liquid or solid aminosilane, described in detail below, to an aqueous solution containing the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I).

[0026] The water-dispersible composition comprises a solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate, defined above in detail. The alkali metal of the siliconate may be chosen from the group consisting of lithium, sodium, potassium, rubidium, cesium, and mixtures thereof. In preferred embodiments, the alkali metal is chosen from the group consisting of lithium, sodium, potassium, and mixtures thereof. In especially preferred embodiments, the alkali metal is chosen from sodium, potassium, and mixtures thereof. In the alkali-metal C ₁ -C ₄ hydrocarbyl siliconate, examples of the C ₁ -C ₄ hydrocarbyl include, without limitation, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl,

1-methylpropyl (isobutyl), 2-methylpropyl (sec-butyl), and 1,1 -dimethyl ethyl (tert-butyl). In preferred embodiments, the C ₁ -C ₄ hydrocarbyl is methyl or ethyl. The solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate may comprise mixtures of one or more alkali-metal C ₁ -C ₄ hydrocarbyl siliconates having different alkali-metal cations and/or different C ₁ -C ₄ hydrocarbyl groups.

[0027] The solvated organosilicon component (II) is derived from at least one

3 1

organosilane having the formula R _x SiZ ₄ - _x , described below in detail. The organosilicon component (II) may be derived from the organosilicon compound, for example, by dissolving the organosilicon compound in an aqueous solution comprising the solvated alkali-metal Ci- C ₄ hydrocarbyl siliconate (I) and the aminosilicon component (III), such that one or more substituents on the organosilicon compound are hydrolyzed. Without intent to be limited by theory, it is believed that solvated organosilicon compounds derived from silanes, for example, may comprise siliconate anions of the general formula represented by the general formula RSi(OH) _a (0 ) _¾ , where R = R and a + b = 3 (as described above in greater detail). These siliconate anions may be charge balanced by alkali-metal cations, such that the organosilicon compound has at least one hydrophobic organic group covalently bonded to a silicon atom.

3 1

[0028] The formula R _x SiZ 4- _x represents at least one organosilane from which the organosilicon compound of the water-dispersible aqueous composition is derived. In the

3 1 1 2

formula R _x SiZ ₄ - _x , each group Z is selected from the group consisting of -OR , -CI, and

2 1

-OH, where R is a C ₁ -C ₄ hydrocarbyl. Thus, non-limiting examples of group Z include, in addition to chloro and hydroxyl groups, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. In general, groups Z are groups that readily hydrolyze in the presence of water, typically being replaced with a hydroxyl group after the hydrolysis.

[0029] In the formula R 3 _x SiZ 1 ₄ - _x , each group R 3 is selected from the group consisting of Ci-Cs hydrocarbyl, C ₃ -C ₈ fluorohydrocarbyl, phenyl, tolyl, and R ⁴ , such that at least one group R in the organosilicon compound is C ₄ -Cs hydrocarbyl, C ₃ -C ₈ fluorohydrocarbyl, or R ⁴ . In preferred embodiments, at least one group R ³ in the organosilicon compound is C ₃ -C ₈ fluorohydrocarbyl.

[0030] Non-limiting examples of Ci-Cs hydrocarbyl groups as options for group R include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, and tert-butyl, and all isomers of pentyl, hexyl, heptyl and octyl. The C ₄ -Cs hydrocarbyl groups among these Ci- Cs hydrocarbyl groups are n-butyl, isobutyl, sec-butyl, and tert-butyl, and all isomers of pentyl, hexyl, heptyl and octyl.

[0031] As further non-limiting examples of R , C ₃ -C ₈ fluorohydrocarbyl groups may be selected from n-propyl groups, n-butyl groups and all isomers of pentyl, hexyl heptyl or octyl groups, in which at least one hydrogen atom, but not all hydrogen atoms are replaced with a fluorine atom. In preferred embodiments, the C ₃ -C ₈ fluorohydrocarbyl group, if present, is linear or branched, but not cyclic. In further preferred embodiments the C ₃ -C6

fluorohydrocarbyl group, if present, may be expressed by the formula -(CH ₂ ) _p -(CF ₂ ) _? -CF ₃ , in which p > 2 and p + q is from 2 to 7. Non- limiting examples of such C ₃ -C6

fluorohydrocarbyls include the 3,3,4,4,5,5,6,6,6-nonafluorohexyl group ("NFH"), in which subscript p is 2 and subscript q is 3; the 3,3,3-trifluoropropyl group ("TFP"), in which subscript p is 2 and subscript q is 0; and the 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, in which subscript p is 2 and subscript q is 5.

3 3

[0032] Group R may be a phenyl group, i.e., an aromatic -C ₆ H ₅ ring. Group R may be a tolyl group, i.e., an aromatic -C ₆ H ₅ ring, in which one hydrogen atom is replaced with a methyl group.

[0033] As noted above, group R ³ in the formula R ³ _x SizVx may be a group R ⁴ . Group R ⁴ has the general structure -R ⁵ -0-(CH ₂ )r _f -R ⁶ , where d is 1 or 2, and in which R ⁵ is a C ₃ linear alkylene or a C ₄ -Cs branched alkylene; and R ⁶ is a Ci-C ₆ perfluoroalkyl. Group R ⁵ may be, for example, n-propylene (-CH ₂ -CH ₂ -CH ₂ -), 2-methylpropylene (-CH ₂ CH(CH ₃ )-CH ₂ -), or 3,3-dimethylpropylene (-CH ₂ CH ₂ -CH(CH ₃ ) ₂ -). Group R ⁶ may be any linear, branched, cyclic, or aromatic alkyl group having from 1 to 6 carbon atoms, the alkyl group being derived from a hydrocarbyl group in which all hydrogen atoms are replaced with fluorine atoms.

[0034] In the group R ⁴ , group R ⁵ is connected on one side to the at least one silane through a carbon-silicon bond and on the opposite side to an oxygen atom. Perfluoroalkyl group R ⁶ is not connected directly to the same oxygen atom; rather, group R ⁶ is connected to a methylene group (-CH ₂ -; d = 1), or an ethylene group (-CH ₂ CH ₂ -; d = 2) that is connected to the oxygen atom. Thus, the portion of group R ⁴ represented by (-R ⁵ -0-(CH ₂ )r _f -) functions as a "spacer group" that isolates the fluorine atoms in the group R ⁶ from the silicon atom in the at least one silane. Without intent to be bound by theory, it is believed that isolation of the perfluoroalkyl groups R ⁶ from the silicon atom adds significant stability to the at least one silane when the at least one silane is added to an aqueous solution containing at least one alkali-metal C ₁ -C ₄ hydrocarbyl siliconate.

[0035] In the formula R 3 _x SiZ 1 ₄ - _x , the subscript x may be 1 , 2, or 3. In preferred

embodiments the subscript x is 1 or 2. In more preferred embodiments the subscript x is 1. The subscript x determines the number of hydrophobic groups R present in the at least one organosilane, relative to the number of easily hydro lyzable groups Z ¹ . Without intent to be bound by theory, it is believed that dissolution of the silanes in the aqueous solution comprising at least one alkali-metal C ₁ -C ₄ hydrocarbyl siliconate results from replacement of the groups Z ¹ with a hydroxyl, a silicone, or a siliconate group. It is believed also that the number of groups R present on the at least one silane determines the type of hydrophobic resin that will form when the water-dispersible composition is exposed to atmospheric carbon dioxide. For example, when subscript x is equal to 1, the silane may form an R Si0 _3/2 unit ("T-unit") in a silsesquioxane resin. When subscript x is equal to 2, the silane may form an R 2S1O2/2 unit ("D-unit") in a resin. When subscript x is equal to 3, the silane may form an R ³ ₃ SiOi _/2 unit ("M-unit") m a resm.

[0036] The water-dispersible composition further comprises a solvated aminosilicon component (III) derived from an aminosilane of the formula R ^A R ⁹ _y SiZ ² ₃ - _y . In the formula 9 2 2 1 1

R R _y SiZ 3-y, each Z is selected from the group consisting of -OR and -OH, where R is a Ci-C ₄ hydrocarbyl. Thus, non- limiting examples of group Z include, in addition to hydroxyl groups, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. In general, groups Z are groups that readily hydrolyze in the presence of water in the water-dispersible aqueous composition, typically being replaced with a hydroxyl group after the hydrolysis. In preferred embodiments, group Z is methoxy or ethoxy. [0037] Group R ⁹ in the formula R ^A R ⁹ _y SiZ ² ₃ - _y , is a Ci ^~ C ₃ hydrocarbyl. Non-limiting examples of group R ⁹ include methyl, ethyl, n-propyl, and 1 -methylethyl (isopropyl).

Preferably, each group R ⁹ is methyl.

[0038] In the formula R^SiZ ² ^, each group R ^A is (-R ⁸ -NR ¹⁰ ) _m -R ⁸ -NR ¹⁰ ₂ , where m is from 0 to 4; R 8 is independently a C ₂ -C ₄ hydrocarbylene; and each R 10 is independently selected from the group consisting of-H and a Ci ^~ C ₃ hydrocarbyl. Subscript m may be 0, 1, 2, 3, or 4. Thus, m + 1 represents the number of nitrogen atoms in the group R ^A .

Q

[0039] Non-limiting examples of group R include ethylene (-CH ₂ -CH ₂ -), n-propylene (-CH ₂ -CH ₂ -CH ₂ -), 1-methylethylene (-CH(CH ₃ )-CH ₂ -), 2-methylethylene

(-CH ₂ -CH(CH ₃ )-), n-butylene (-CH ₂ -CH ₂ -CH ₂ -CH ₂ -), 1-methylpropylene

(-CH(CH ₃ )-CH ₂ -CH ₂ -), 2-methylpropylene (-CH ₂ -CH(CH ₃ )-CH ₂ -; isobutylene), 1,1-dimethylethylene (-C(CH ₃ )(CH ₃ )-CH ₂ -), 2,2-dimethylethylene (-CH ₂ -C(CH ₃ )(CH ₃ )-);

Q

and 1 ,2-dimethyl ethylene (-CH(CH )-CH(CH )-). In preferred embodiments, group R is n-propylene or isobutylene and acts as a spacer group between the silicon atom and nitrogen

8 A.

atoms, with one group R connecting group R as a whole to the silicon atom.

[0040] Non-limiting examples of group R ¹⁰ include methyl, ethyl, n-propyl, and

1 -methylethyl (isopropyl). Preferably, each group R ¹⁰ is hydrogen or methyl. In preferred embodiments, m is 0, such that group R ^A is -R ⁸ -NR ¹⁰ ₂ . In an especially preferred example,

10 8

m is 0; each R is hydrogen; and R is n-propylene.

[0041] In the formula R ^A R ⁹ _y SiZ ² ₃ - _y , subscript y is 0, 1 or 2. The subscript 3 ^~ y represents the number of hydrolysable groups Z in the aminosilane and can equal 1, 2, or 3. Thus, each aminosilane from which the solvated aminosilicon component (III) is derived contains one amine-containing group R ^A ; one or two Ci-C ₃ hydrocarbyl groups R ⁹ , preferably all methyl; and one, two, or three hydrolysable groups Z ² , provided the total number of groups R ^A , R ⁹ , and Z is four. In preferred embodiments, y is 1, and 3 ^~ y is 2. An example of a preferred aminosilane according to the formula R ^A R ⁹ _y SiZ ² ₃ -y includes 3-aminopropyl- methyldiethoxysilane, for which R ^A is (-R ⁸ -NH ₂ ) _m -R ⁸ -NR ¹⁰ ₂ where m is 0, R ⁸ is

10 9 2 2 2

n-propylene, and each R is hydrogen; R is methyl; each Z is -OR , where R is ethyl; and y is 1.

[0042] In the water-dispersible composition, the solvated organosilicon component (II) and the solvated aminosilicon component (III) are formed by adding the organosilicon compound(s) and the aminosilane(s) to an aqueous solution comprising the alkali-metal Ci- C ₄ hydrocarbyl siliconate (I). The addition of the organosilicon compound(s) and the aminosilane(s) to the aqueous solution can occur sequentially or simultaneously, as well as in continuous or batch configurations, as described below in greater detail. If the addition is sequential, preferably the aminosilane(s) is added to the aqueous solution first, followed by addition of the organosilicon compound(s). If the addition is simultaneous, preferably the organosilicon compound(s) and the aminosilane(s) are mixed in a first vessel, and then the resulting mixture of organosilicon compound(s) and aminosilane(s) is added to the aqueous solution in a second vessel. The addition may occur by any practical means and preferably occurs drop-wise.

[0043] Substantial or complete solvation of the organosilicon compound may require heating of a mixture of the alkali-metal C ₁ -C ₄ hydrocarbyl siliconate, the organosilicon compound, and the aminosilane to a temperature of greater than 50 °C, preferably greater than 80 °C, for a period of time such as, for example, 1 to 5 hours, 24 hours, or even up to 72 hours, depending on the organosilicon compound being solvated. Additionally, solvation of the organosilicon compound may require physical manipulation of the mixture, such as by mixing, stirring, rolling, shaking, or agitating the mixture while the mixture is held at the elevated temperature for a period of time.

[0044] The amount of hydrocarbyl-substituted, fluoroalkyl-substituted or phenyl- substituted silanes that may be solvated as the organosilicon component (II) in water- dispersible aqueous compositions comprising alkali-metal C ₁ -C ₄ hydrocarbyl siliconates depends on the chain length of the hydrocarbyl or fluoroalkyl group and the concentrations of the alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I) and aminosilicon component (III) in solution. For example, when the organosilicon compound comprises NFH groups as group R , it is believed that a practical limit of solvated components in the water-dispersible aqueous composition is reached at about 20 wt.% solvated organosilicon component (II) in 40 wt.% solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I), based on the total weight of the water-dispersible aqueous composition.

[0045] Though certain organosilicon compounds may solvate to a level of greater than 20 wt.%), based on the total weight of the water-dispersible aqueous composition, such compositions may have poor stability on dilution. In general, it is believed that lower concentrations of solvated organosilicon component in the water-dispersible aqueous composition results in a higher level of stability on dilution. In preferred embodiments, the water-dispersible aqueous composition may comprise about 5 wt.% to about 10 wt.% of the solvated organosilicon component (II), about 40 wt.% of the solvated alkali -metal C ₁ -C ₄ hydrocarbyl siliconate (I), and from about 0.5 wt.% to about 15 wt.% of the aminosilicon component (III), based on the total weight of the water-dispersible aqueous composition, with water or other water-soluble inert ingredients being the balance.

[0046] In examples of water-dispersible aqueous compositions, the water-dispersible composition may comprise, based on the total weight of the water-dispersible composition, from 30 wt.% to 60 wt.% of the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I); from

1 wt.%) to 20 wt.%) of the solvated organosilicon component (II); and from about 0.5 wt.% to about 20 wt.% of the solvated aminosilicon component (III). In preferred examples, the water-dispersible composition may comprise from about 35 wt.% to about 50 wt.% of the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I); from about 2 wt.% to about 15 wt.%, or from about 2 wt.% to about 10 wt.%, of the solvated organosilicon component (II); and from about 1 wt.% to about 15 wt.%, or from about 1 wt.% to about 10 wt.%, or from about

2 wt.% to about 15 wt.%, or from about 5 wt.% to about 10 wt.% of the solvated aminosilane component (III).

[0047] In preferred examples of water-dispersible aqueous compositions, the weight ratio of the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I) to the solvated organosilicon component (II) in the water-dispersible composition may be from about 3 : 1 to about 50: 1, preferably from about 4: 1 to about 40: 1. In preferred examples of water-dispersible aqueous compositions, the weight ratio of the solvated organosilicon component (II) to the solvated aminosilicon component (III) in the water-dispersible composition may be from about 0.5: 1 to about 3: 1, preferably from about 1 : 1 to about 2: 1. Moreover, preferred examples of water- dispersible aqueous compositions may have a "total-solids content," defined as the total weight portion of the composition derived from the combination of the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I), the solvated organosilicon component (II), and the solvated aminosilane component (III) of from about 30 wt.% to about 70 wt.%.

[0048] The water-dispersible aqueous compositions preferably are dilution stable, such that part aqueous composition may be diluted in from 1 part to 100 parts of a diluent such as water to yield diluted water-dispersible aqueous compositions. Preferred diluted water- dispersible aqueous compositions may comprise, for example, from about 0.3 wt.% to about 1 wt.% of the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate (I); from about 0.01 wt% to about 0.2 wt.% of the solvated organosilicon component (II); and from about 0.01 wt.% to about 0.2 wt.% of the solvated aminosilane component (III). Preferred examples of diluted water-dispersible aqueous compositions may have total-solids contents of from about 0.1 wt.%) to about 15 wt.%, more preferably from about 0.3 wt.% to about 10 wt.%, still more preferably from about 0.5 wt.% about 5 wt.% or from about 0.5 wt.% to about 3 wt.%. [0049] Further embodiments are directed to methods for forming the water-dispersible aqueous compositions described above. In example methods for forming the water- dispersible aqueous compositions, at least one organosilicon compound (in solid or liquid form) and at least one aminosilane (in solid or liquid form) are reacted with an aqueous solution comprising a solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate to form a reaction mixture. The reacting may be accomplished according to various configurations including, but not limited to, the embodiments described below.

[0050] In one example embodiment, the reacting of the at least one organosilicon compound with the aqueous solution may occur in a single step configuration by simply adding the organosilicon compound and the aminosilane to a vessel containing the aqueous solution comprising a solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate.

[0051] In another example embodiment, in a batch configuration, the reacting may comprise a further step prior to the reacting, wherein the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate is formed by adding a silane of the formula R^SiXs to an aqueous solution comprising an alkali-metal hydroxide such as potassium hydroxide or sodium hydroxide. Thereupon, the organosilicon compound and the aminosilane may be added to the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate thus formed, to form the reaction mixture.

[0052] In still another example embodiment, the reacting of the at least one organosilicon compound with the aqueous solution may occur in a continuous configuration. In a continuous configuration, water, alkali-metal hydroxide, a silane of the formula R^SiXs, the aminosilane, and the organosilicon compound each may be added to a single vessel. In the silane of the formula R^SiXs, R ¹ is a C ₁ -C ₄ hydrocarbyl, defined as above; and each X is a hydrolyzable group such as, for example, halogens or groups -OZ, where Z is hydrogen or a C ₁ -C ₄ hydrocarbyl. This configuration results in formation of the solvated alkali-metal Ci- C ₄ hydrocarbyl siliconate in solution and the reacting of the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate with the organosilicon compound and the aminosilane in the same solution.

[0053] Regardless of the configuration, in the reacting step to form the reaction mixture, the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate is as defined above with regard to the embodiments of water-dispersible aqueous compositions. The organosilicon compound is at

3 1 1

least one silane having a formula R _x SiZ ₄ - _x , where each Z is selected from the group

2 2 3 consisting of -OR , -CI, and -OH; each R is a Ci-C ₄ hydrocarbyl; each R is selected from the group consisting of Ci-Cs hydrocarbyl, C3-C8 fluorohydrocarbyl, phenyl, tolyl, and R ⁴ , such that at least one group R in the organosilicon compound is C ₄ -Cs hydrocarbyl, C ₃ - Csfluorohydrocarbyl, or R ⁴ ; R ⁴ is -R ⁵ -0-(CH ₂ ) _d -R ⁶ ; R ⁵ is a C ₃ linear alkylene or a C ₄ -C5 branched alkylene; R ⁶ is a Ci-C ₆ linear or branched perfluoroalkyl; and x is 1, 2, or 3. The aminosilane is at least one compound having the formula R ^A R ⁹ _y SiZ ² ₃ - _y , where each Z ² is selected from the group consisting of -OR ⁷ , and -OH; each R ⁷ is a C ₁ -C ₄ hydrocarbyl; each R ^A is (-R ⁸ -NR ¹⁰ ) _m -R ⁸ -NR ¹⁰ ₂ , where m is from 0 to 4; each R ⁸ is independently a C ₂ -C ₄ hydrocarbylene; each R ⁹ is a Ci ^~ C ₃ hydrocarbyl; each R ¹⁰ is independently selected from the group consisting of -H and Ci ^~ C ₃ hydrocarbyl; and y is 0, 1 or 2. Each of the R groups may be defined as above with respect to the water-dispersible compositions.

[0054] The aqueous solution may comprise from about 20 wt.% to about 60 wt.%, preferably from about 30 wt.% to about 50 wt.%, more preferably from about 35 wt.% to about 45 wt.% of the solvated alkali-metal Ci-C ₄ hydrocarbyl siliconate, based on the total weight of the aqueous solution. Preferably, an amount of the organosilicon compound is added to the aqueous solution, such that the reaction mixture comprises from about 1 wt.% to about 20 wt.%, preferably from about 2 wt.% to about 15 wt.%, more preferably from about 5 wt.% to about 10 wt.% of the organosilicon compound. Likewise, preferably an amount of the aminosilane is added to the aqueous solution, such that the reaction mixture comprises from about 0.5 wt.% to about 20 wt.%, preferably from about 2 wt.% to about 15 wt.%, more preferably from about 5 wt.% to about 10 wt.% of the aminosilane. The addition of the organosilicon compound and the aminosilane to the aqueous solution may occur in any suitable reaction vessel, such as a laboratory-scale jar, beaker, or flask, or an industrial-scale reactor, provided the reaction vessel is chemically inert to the alkali-metal C ₁ -C ₄ hydrocarbyl siliconate, the organosilicon compound, and the aminosilane.

[0055] The method for forming the water-dispersible aqueous compositions further may comprise heating the reaction mixture to a reaction temperature of from 50 °C to 150 °C. In preferred embodiments, the reaction mixture is heated to a reaction temperature of from 80 °C to 120 °C. A higher reaction temperature of at least 80 °C may be preferred to minimize the amount of time necessary for the organosilicon compound and the aminosilane to react with the alkali-metal Ci-C ₄ hydrocarbyl siliconate and to dissolve in the aqueous solution.

[0056] The method for forming the water-dispersible aqueous compositions further may comprise manipulating the reaction mixture until the organosilicon compound and the aminosilane are completely dissolved in the reaction mixture. The manipulating may involve any practical form of manipulation such as, for example, mixing, stirring, rolling, shaking, agitating, or sonicating. Typically, the reaction mixture is manipulated while the reaction temperature of from 50 °C to 150 °C is maintained. The most reactive organosilicon compounds may require no manipulation to react and dissolve in the reaction mixture.

Solvation of less-reactive organosilicon compounds may require the reaction mixture to be manipulated for up to 72 hours. Typically, the organosilicon compounds dissolve completely within the reaction mixture after from 1 hour to 24 hours of manipulation at the reaction temperature of from 50 °C to 150 °C. Preferred water-dispersible aqueous compositions comprise alkali-metal C ₁ -C ₄ hydrocarbyl siliconates and organosilicon components that both are completely solvated. As such, organosilicon components that do not completely dissolve within the reaction mixture after 72 hours of manipulation of the reaction mixture at the reaction temperature of from 50 °C to 150 °C are not preferred.

[0057] Optionally, the method for forming the water-dispersible aqueous compositions further may comprise aging the reaction mixture at any stage for a sufficient amount of time to maximize the amount of product formed. Optionally, the method for forming the water- dispersible aqueous compositions further may comprise removal of hydrolysis byproducts such as alcohols from the reaction mixture. Removal of the byproducts may occur by distillation or other appropriate means. The removal of the byproducts may purify the water- dispersible composition or may reduce the flammability of the water-dispersible composition, particularly when alcohols are removed.

[0058] Further embodiments are directed to methods for treating a substrate surface using at least one of the water-dispersible aqueous compositions described above. The substrate surface is typically an outer surface of a substrate. The substrate may be any porous material for which sealing or waterproofing of a surface of the substrate is desirable such as a porous construction material, for example. Examples of such substrates include, but are not limited to, brick, stone, masonry, concrete, asphalt, wood, gypsum, paper, combinations thereof, and assemblies or materials comprising any of these such as, for example, sidewalks, wallboard, and roofing shingles.

[0059] In the method for treating the substrate surface, a coating of a water-dispersible aqueous composition is applied to the substrate surface to form a treated substrate surface. The water-dispersible aqueous composition may comprise a total-solids content of from about 0.1 wt.% to about 45 wt.%, for example from about 0.1 wt.% to about 45 wt.%, based on the total weight of the water-dispersible aqueous composition. The total-solids content is derived from the amount of the water-dispersible aqueous composition consisting of a combination of a solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate, a solvated organosilicon component, and a solvated aminosilicon component. [0060] The solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate is as defined above with respect to the water-dispersible composition. The organosilicon compound is at least one

3 1 1

silane having a formula R _x SiZ ₄ - _x , where each Z is selected from the group consisting of

2 2 3

-OR , -CI, and -OH; each R is a Ci-C ₄ hydrocarbyl; each R is selected from the group consisting of Ci-Cs hydrocarbyl, C ₃ -C8 fluorohydrocarbyl, phenyl, tolyl, and R ⁴ , such that at least one group R in the organosilicon compound is C ₄ -Cs hydrocarbyl, Ci-C ₆

fluorohydrocarbyl or R ⁴ ; R ⁴ is -R ⁵ -0-(CH ₂ )r _f -R ⁶ , where i is 1 or 2; R ⁵ is a C ₃ linear alkylene or a C ₄ -C ₅ branched alkylene; R ⁶ is a Ci-C ₆ perfluoroalkyl; and x is 1, 2, or 3. The aminosilane is at least one compound having the formula R ^A R ⁹ _y SiZ ² 3- _y , where each Z ² is selected from the group consisting of -OR ⁷ , -CI, and -OH; each R ⁷ is a Ci-C ₄ hydrocarbyl; each R ^A is (-R ⁸ -NR ¹⁰ ) _m -R ⁸ -NR ¹⁰ ₂ , where m is from 0 to 4; each R ⁸ is independently a C ₂ -C ₄ hydrocarbylene; each R ⁹ is a C ₁ -C ₃ hydrocarbyl; each R ¹⁰ is independently selected from the group consisting of -H and C ₁ -C3 hydrocarbyl; and y is 0, 1 or 2. Each of the R groups may be defined as above with respect to the water-dispersible compositions.

[0061] The weight ratio of the solvated alkali-metal Ci-C ₄ hydrocarbyl siliconate to the solvated organosilicon component in the water-dispersible composition may be from 3 : 1 to 50: 1, preferably from 4: 1 to 30: 1 , more preferably from 4: 1 to 40: 1. The weight ratio of the solvated organosilicon component to the aminosilicon component in the water-dispersible composition may be from 0.5 : 1 to 3 : 1 , preferably from about 1 : 1 to about 2: 1.

[0062] The coating of the water-dispersible aqueous composition may be applied to the substrate surface by any practical means, using any suitable applicator. For example, the coating may be applied by brushing, rolling, or spraying. In the case of relatively small articles, such as bricks or blocks, the composition may be applied by dipping. Preferably, the composition is applied to the substrate surface at a coverage of from 50 g to 500 g of water- dispersible aqueous composition per square-meter of substrate surface to facilitate even coverage and penetration. At this level of coverage, the coating may have a depth of penetration of from about 0.1 mm to about 10 mm, for example, depending upon the porosity of the substrate and amount of treatment contained in the composition. Additional benefits may be realized by multiple applications to the substrate surface after a first coating is allowed to dry

[0063] After the coating of the water-dispersible aqueous composition is applied, the treated substrate surface is exposed naturally to atmospheric carbon dioxide to form a hydrophobic and— in the case when R is fluorohydrocarbyl, additionally oleophobic— sealing layer within the treated substrate surface. Without intent to be limited by theory, it is believed that the hydrophobic and optionally oleophobic sealing layer may comprise an alkali metal carbonate derived from the alkali-metal C ₁ -C ₄ hydrocarbyl siliconate and a silicone resin derived from the organosilicon component and the aminosilicon component. The hydrophobic and optionally oleophobic sealing layer may further comprise at least one carbonate compound derived from the organosilicon component or the aminosilicon component. Likewise, the silicone resin may comprise at least one structural unit derived from the alkali-metal C ₁ -C ₄ hydrocarbyl siliconate. Regardless, the treated substrate surface, after exposure to atmospheric carbon dioxide, comprises a silicon resin. The hydrophobic and optionally oleophobic sealing penetrant may be effective at sealing and protecting the substrate against permeation and staining by both polar and in the case of the optionally oleophobic penetrant, non-polar substances.

[0064] When a silane-based organosilicon compound is incorporated in the water- dispersible aqueous composition, the silicon resin formed after exposure to atmospheric carbon dioxide may comprise at least one group R , defined as above, imparts hydrophobicity and in the case of R being fluorohydrocarbyl, oleophobicity to the treated substrate surface. Depending on the choice of group R in the organosilicon compound, drops of both polar and non-polar liquids may bead up on the sealing layer with a static contact angle of greater than 90°.

[0065] Example methods of treating the substrate surface may further comprise diluting a concentrated water-dispersible aqueous composition before the applying of the coating to form the water-dispersible aqueous composition. The concentrated water-dispersible aqueous composition may be acquired by an end-user, for example, after being prepared and packaged by a supplier, for example, and may comprise a total-solids content of from 20 wt.% to 60 wt.%, based on the total weight of the concentrated water-dispersible aqueous

composition. The total-solids content of the concentrated water-dispersible aqueous composition may comprise, consist essentially of, or consist of the combination of the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate, the solvated organosilicon component, and the solvated aminosilicon component. Diluting the concentrated water-soluble aqueous composition may comprise adding a sufficient amount of water to the concentrated water- dispersible aqueous composition, such that the water-dispersible aqueous composition comprises a total-solids content of from about 0.1 wt.% to about 45 wt.%, for example from 0.1 wt.%) to 10 wt.%), based on the total weight of the water-dispersible aqueous composition, wherein the total-solids content may comprise, consist essentially of, or consist of the combination of the solvated alkali-metal C ₁ -C ₄ hydrocarbyl siliconate, the solvated organosilicon component, and the aminosilicon component.

EXAMPLES

[0066] The present invention will be better understood by reference to the following examples, which are offered by way of illustration and which one of skill in the art will recognize are not meant to be limiting. In the following examples, Compound A refers to Dow-Corning ^® 777 water repellent, an aqueous mixture of 42% w/w potassium

methylsilanetriolate (CAS No. [31795-24-1]), 0.9% w/w methanol, and 57.1% w/w water. Potassium methylsilanetriolate is also known as potassium methyl siliconate.

Comparative Example 1

[0067] Compound A (100 g) was charged into a 250-mL round glass bottle, to which nonafluoro-hexyltrimethoxysilane (3.09 g) was added. A magnetic stir bar was added to the bottle contents, and the bottle was purged with nitrogen and sealed with a plastic screw cap. The contents then were stirred overnight at room temperature to yield a hazy solution. Some precipitation was observed on storage.

Comparative Example 2

[0068] Compound A (42.04 g) was charged into a round-bottom flask fitted with an overhead stirrer, a condenser, a heating mantle and a dropping funnel. Nonafluoro- hexyltrimethoxysilane (4.08 g) was added to the dropping funnel. The contents of the round- bottom flask were heated to 50 °C under nitrogen, after which the

nonafluorohexyltrimethoxysilane was added drop-wise. After the drop-wise addition was complete, the solution was held at 50 °C for an additional three hours and then was cooled. After the cooling, a clear solution remained. The clear solution developed some minor particle precipitation on standing. Dilution of the sample with water to a solids content of 5.0%) (w/w), then further to 0.5%> (w/w), resulted in hazy solutions. Some precipitation was observed on storage.

Comparative Example 3

[0069] A solution of potassium hydroxide (45% w/w solution - 36.48 g) and water (31.02 g) was charged into a round-bottom flask fitted with an overhead stirrer, a condenser, a heating mantle, and a dropping funnel. Methyltrimethoxysilane (17.5 g) and nonafluorohexyl-trimethoxysilane (15.4 g) were charged into the dropping funnel. The contents of the round-bottom flask were heated to 30 °C under nitrogen, after which the contents of the dropping funnel were added drop-wise. After the drop-wise addition was completed, the solution was left at 30 °C for an additional hour. After the hour, the reaction contents were heated to 115 °C with an applied vacuum of 800 mbar to strip off the water and volatiles. The contents were cooled, and the resulting concentrate was diluted with water to provide a solid content of 42% (w/w). During the cooling and on storage, significant precipitation of the reaction product was observed.

Comparative Example 4

[0070] A solution of potassium hydroxide (45% w/w solution - 36.44 g) and water (31.02 g) was charged into a round-bottom flask fitted with an overhead stirrer, a condenser, a heating mantle, and a dropping funnel. Methyltrimethoxysilane (22.5 g) and

nonafluorohexyl-trimethoxysilane (10.02 g) were charged into the dropping funnel. The contents of the round-bottom flask were heated to 30 °C under nitrogen, after which the contents of the dropping funnel were added drop-wise. After the drop-wise addition was completed, the solution was left at 30 °C for an additional hour. After the hour, the reaction contents were heated to 115 °C with an applied vacuum of 800 mbar to strip off the water and volatiles. The contents were cooled, and the resulting concentrate was diluted with water to provide a solid content of 42% (w/w). During the cooling and on storage, significant precipitation of the reaction product was observed.

Comparative Example 5

[0071] A solution of potassium hydroxide (45%w/w solution - 36.48 g) and water (31.02 g) was charged into a round-bottom flask fitted with an overhead stirrer, a condenser, a heating mantle and a dropping funnel. Methyltrimethoxysilane (27.5 g) and nonafluoro- hexyltrimethoxysilane (5.0 g) were charged into the dropping funnel. The contents of the round-bottom flask were heated to 30 °C under nitrogen, after which the contents of the dropping funnel were added drop-wise. After the drop-wise addition was completed, the solution was left at 30 °C for an additional hour. After the hour, the reaction contents were heated to 115 °C with an applied vacuum of 800 mbar to strip off the water and volatiles. The contents were cooled, and the resulting concentrate was diluted with water to provide a solid content of 42% (w/w). During the cooling and on storage, some precipitation of the reaction product was observed. Example 1

[0072] Compound A (41.06 g) was charged into a round-bottom flask fitted with an overhead stirrer, a condenser, a heating mantle, and a dropping funnel. Nonafluoro- hexyltrimethoxy silane (4.3 g) and aminopropylmethyldiethoxysilane (5.2 g) were charged into the dropping funnel. The contents of the round-bottom flask were heated to 80 °C under nitrogen, after which the contents of the dropping funnel were added drop-wise. After the drop-wise addition was completed, the solution was left at 80 °C for an additional three hours, after which the solution was cooled. After cooling and on standing, no precipitation of the modified potassium methylsilanetriolate was observed. The material was diluted with water to a solid content of 3% (w/w), and further to a solid content of 0.5% (w/w) and was found to be dilution stable.

Example 2

[0073] Compound A (43.5 g) was charged into a round-bottom flask fitted with an overhead stirrer, a condenser, a heating mantle, and a dropping funnel. Nonafluoro- hexyltrimethoxy silane (4.0 g) and aminopropylmethyldiethoxysilane (2.3 g) were charged into the dropping funnel. The contents of the round-bottom flask were heated to 80 °C under nitrogen, after which the contents of the dropping funnel were added drop-wise. After the drop-wise addition was completed, the solution was left at 80 °C for an additional three hours, after which the solution was cooled. After cooling and on standing, no precipitation of the modified potassium methylsilanetriolate was observed. The material was diluted with water to a solid content of 3% (w/w) and further to a solid content of 0.5% (w/w) and was found to be dilution stable.

Example 3

[0074] Compound A (37.5 g) was charged into a round-bottom flask fitted with an overhead stirrer, a condenser, a heating mantle, and a dropping funnel.

3,3,4,4,5,5,6,6,7,7,8,8,8 -tridecaf uorooctyl trimethoxysilane (10.0 g) and

aminopropylmethyldiethoxysilane (2.5 g) were charged into the dropping funnel. The contents of the round-bottom flask were heated to 80 °C under nitrogen, after which the contents of the dropping funnel were added drop-wise. After the drop-wise addition was completed, the solution was left at 80 °C for an additional three hours, after which the solution was cooled. After cooling and on standing, no precipitation of the modified potassium methylsilanetriolate was observed. The material was diluted with water to a solid content of 3% (w/w) and further to a solid content of 0.5% (w/w) and was found to be dilution stable.

Performance Characterizations of Compositions

[0075] The materials prepared in Examples 1-3 with varying solid contents each were applied to 3-inch x 4-inch (7.6 cm x 10.2 cm) pieces of brick tile at a coverage of

approximately 300 g/m . The samples then were allowed to dry for 48 hours at room temperature. After the samples were dried, several staining agents were applied to the surface and left in contact with the surface for 24 hours. The staining agents used were olive oil (Fillippo Berio brand, amber yellow in color, used straight from the bottle); black coffee (prepared by adding about 2.5 g Nescafe ^® brand dark-roast instant coffee to 100 mL cold water); black tea (prepared by steeping a Pg Tips brand teabag in boiling water for

10 minutes); red wine (a carbernet sauvignon used straight from a bottle); cola (Diet Coke ^® brand cola, used straight from a can); and tomato ketchup (Heinz ^® brand tomato ketchup used straight from a bottle).

[0076] After the 24 hours of contact of the staining agent with the treated surface, the staining agents were removed with a wet cloth. The surfaces that were in contact with the stain then were assessed for their resistance to staining. Stain-resistance was rated on a scale of 1 to 5, with a rating of 1 indicating considerable surface staining and a rating of 5 indicating no surface staining. The stain-resistance ratings were compiled and are shown in TABLE 1.

2

TABLE 1 : Staining behavior of a brick-tile substrate treated with coverage of 300 g/m

[0077] The water pick-up behavior of the brick tiles was determined by first saturating the surfaces of the brick tile with the materials prepared in Examples 1 and 2 with solid contents of 0.5% (w/w), subsequently allowing the brick tiles to dry for 24 hours, and then immersing the brick tiles in water for 24 hours. The weight of water uptake was recorded as a percentage of the brick tile weight. These data are provided in TABLE 2.

TABLE 2: Water uptake of treated brick-tile substrates

[0078] Additionally, static contact angles of a polar solvent (water) and a non-solvent (hexadecane) were measured on the treated substrates based on a drop size of 1 μί. Data from the static contact angle measurements on the brick-tile substrates are compiled in TABLE 3.

TABLE 3: Static contact angle of liquids on treated brick-tile substrates.

[0079] Generally, a static contact angle near or greater than 90° for a given liquid indicates a surface upon which the given liquid cannot spread but, rather, on which the given liquid forms beads. Conversely, a static contact angle of less than 90° for a given liquid indicates a surface upon which the given liquid does spread. A static contact angle cannot be measured for a liquid which soaks into the substrate. For an untreated brick-tile both water and hexadecane soak into the surface. The data in TABLE 3 show that the compositions produced a treated surface that was hydrophobic and oleophobic.

Staining Behavior on Additional Substrates

[0080] The materials prepared in Example 3 with a solids content of 3.0% w/w each were applied to concrete blocks (each approximately 2 inches (5.08 cm) by 4 inches (10.2 cm)) that had been aged for 30 days after preparation; to chiffon- white granite pieces (each approximately 3 inches (7.62 cm) by 5 inches (12.7 cm)); and to jet-black marble pieces (each approximately 3 inches (7.62 cm) by 5 inches (12.7 cm)). The composition of Example 3 with a solids content of 3.0% w/w was applied at a coverage of about 300 g/m for the

2 2

concrete substrate, about 100 g/m for the granite, and about 50 g/m for the marble test pieces. The samples then were allowed to dry for 48 hours at room temperature. After the samples were dried, several staining agents were applied to the surface and left in contact with the surface for 24 hours as described above.

[0081] Staining behaviors of the various substrates treated with the 3.0% w/w composition of Example 3 are summarized in TABLE 4. The water uptakes of the same substrates are summarized in TABLE 5. The static contact-angle measurements of the same substrates are summarized in TABLE 6. The data in TABLES 4-6 were acquired in the same manner as described above for the brick-tile substrates.

TABLE 4: Staining behavior of 3.0% w/w Example 3 composition on various substrates

TABLE 5: Water uptake of substrates treated with 3.0% w/w composition of Example 3

TABLE 6: Static contact angle measurements of liquids applied to substrates treated with

3.0%) w/w composition of Example 3

[0082] The data in TABLES 4-6 indicate favorable staining behavior, water uptake, oleophobicity and hydrophobicity characteristics on each of the additional substrates.

[0083] Though particular embodiments have been illustrated, described, and/or exemplified, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.