WO2016176386A1

WO2016176386A1 - Architectural coatings containing fluorinated polymeric additives

Info

Publication number: WO2016176386A1
Application number: PCT/US2016/029660
Authority: WO
Inventors: Anilkumar Raghavanpillai; James J. Hughes; Brad M. Rosen; John Russell Crompton, Jr.; Vincent FRANCO
Original assignee: The Chemours Company Tt, Llc
Priority date: 2015-04-30
Filing date: 2016-04-28
Publication date: 2016-11-03

Abstract

The present invention comprises a composition and method of use for providing cleanability to architectural coatings. Such compositions comprise a coating base and a fluoropolymer additive, such that the coatings additive is allowed to migrate to the coating surface and further cure once applied to a substrate. The compositions of the present invention provide durability to coating compositions, while also providing surface effects such as increased water and oil contact angles, enhanced dirt pickup resistance, and enhanced cleanability to the coating films.

Description

TITLE OF INVENTION

ARCHITECTURAL COATINGS CONTAINING FLUORINATED POLYMERIC ADDITIVES

FIELD OF THE INVENTION

This invention relates to a composition containing a coating base and a fluorinated polymer compound for use in architectural coating compositions such as water-based latex paints, to provide lasting surface effects.

BACKGROUND OF THE INVENTION

The coating compositions of interest in the present invention include alkyd coating compositions, urethane coating compositions, water- dispersible coating compositions, and unsaturated polyester coating compositions, typically a paint, clear coating, or stain. All of the above- listed coating compositions after drying or curing often show low

hexadecane contact angles, are readily wetted by oil, and are susceptible to soiling. The coating compositions are described in Outlines of Paint Technology (Halstead Press, New York, NY, Third edition, 1990) and Surface Coatings Vol. I, Raw Materials and Their Usage (Chapman and Hall, New York, NY, Second Edition, 1984).

Fluorinated polymer compositions are used in the preparation of a wide variety of surface treatment materials to provide surface effects to substrates. Many such compositions are fluorinated acrylate polymers or copolymers which contain predominantly eight or more carbons in the perfluoroalkyl chain to provide the desired properties. Honda, et al., in Macromolecules, 2005, 38, 5699-5705 teach that for perfluoroalkyl chains of greater than 8 carbons, orientation of the perfluoroalkyl groups, designated Rf groups, is maintained in a parallel configuration while for such chains having 6 or less carbons, reorientation occurs. This reorientation is recited to decrease surface properties such as contact angle. Thus, polymers containing shorter perfluoroalkyl chains have traditionally not been commercially successful. BRIEF SUMMARY OF THE INVENTION

Water-based latex coating bases, such as those employed as paint coatings, have a tendency to have low oil repellency and poor cleanability ratings. To impart better cleanability to interior and exterior paint surfaces, small molecule additives, including fluorosurfactants, have been used. Due to their small molecular size, however, the additives do not provide long-term performance and durability in exterior paint, which is subjected to more extreme environmental conditions. The additives can wash away from the coating surface within a few days.

The present invention addresses the issues described above by introducing polymeric compounds comprised of fluoroalkyl (meth)acrylate copolymers with phosphate-, phosphonate- or silane-group containing monomers, such that the polymer compound may anchor onto

components in the coating composition. Additional repeat units may be present in the polymer, such as an olefin-containing long-chain

hydrocarbons. Such a crosslinkable group may polymerize with other polymeric additive molecules (ethylenic unsaturated groups) or with other components of the coating composition. Due to the polymeric and anchoring nature of the fluoropolymer additive, the compositions of the present invention provide performance as well as durability to the water- based latex coatings. Additionally, the low molecular weight allows the polymers to migrate to the coating surface before anchoring to form a durable additive at the coating surface. The polymers of the invention impart unexpectedly desirable surface effects such as: increased water and oil contact angles, enhanced dirt pickup resistance, and enhanced cleanability to the coating films.

The present invention comprises a composition comprising (a) a coating base selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and (b) a polymer compound comprising the repeat Units A, B, and C, and optionally Unit D in any order:

Unit A Unit B Unit e Unit D where Rf is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -0- , -CH2-, -CFH-, or combinations thereof; A is 0, S, or N(R²); Q is a straight chain, branched chain or cyclic structure of alkylene, alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups; R¹ is H or CH3; R² is independently selected from H or a linear or branched alkyl of 1 to about 4 carbon atoms; R⁴ is H, an alkyl of 1 to 4 carbon atoms, or - C(0)OR¹¹ ; X is -C(0)0- -C(O)-, -R⁷0-, -C(0)OR⁷NHC(0)NH-, or -

R⁷OC(0)-; R⁶ is a straight or branched alkylene of 1 to 5 carbon atoms; R⁷ is a straight or branched alkylene of 1 to 5 carbon atoms; V is - OP(0)(OR⁸)(OR⁹), -P(0)(OR⁸)(OR⁹), or -Si(L¹)_x(L²)₃-_x; v, s, and t are independently 0 or 1 ; R⁸ and R⁹ are independently H, HN(R²)3, or straight or branched alkyls of 1 to 5 carbon atoms; L¹ and L² are independently selected from R¹⁰ or OR¹⁰; x is 0 to 3; R¹¹ is H or straight or branched alkyls of 1 to 5 carbon atoms; R¹⁰ is a straight or branched alkyl of 1 to 4 carbon atoms; Z is selected from H, Na, Li, Cs, K, HN(R²)3, a hydroxy- terminated straight or branched alkyl of 1 to 10 carbons, or a hydroxy- terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units, or mixtures thereof; Y is selected from -CH2O-, -C(0)0-, -OC(O)-, - R⁵OC(0)-, -C(0)0(CH2CH20)m(CH2CH(CH₃)0)n- or -C(0)OR⁵0-; R⁵ is a straight or branched alkylene of 1 to 10 carbons; m and n are

independently integers of 0 to 20, provided that m+n>0; R³ is a straight or branched alkyl chain of 1 to 30 carbons, optionally having at least one olefinic unit, or mixtures thereof; Unit A is present in an amount of about 10 to 60 mol %; Unit B is present in an amount of about 1 to 30 mol%; Unit C is present in an amount of about 1 to 50 mol%; and Unit D is present in an amount of 0 to 40 mol%; wherein the sum of repeat units is equal to 100 mol%; and wherein the composition comprises (a) the coating base in an amount of from about 95 to 99.98% and (b) the polymer compound in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b).

In another embodiment, the invention comprises a process for forming a coating with improved cleanability comprising

a. contacting (a) a coating base comprising a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; with (b) a polymer compound to form a coating composition;

b. applying the coating composition to a substrate to form a coating; and

c. allowing the polymer compound to migrate to the coating surface;

wherein the polymer compound comprises the repeat Units A, B, and C, and optionally Unit D in any order; where Rf is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -0-, -CH2-, -CFH-, or combinations thereof; A is O, S, or N(R²); Q is a straight chain, branched chain or cyclic structure of alkylene, alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups; R¹ is H or CH3; R² is independently selected from H or a linear or branched alkyi of 1 to about 4 carbon atoms; R⁴ is H, an alkyi of 1 to 4 carbon atoms, or -C(0)OR¹¹ ; X is -C(0)0- -C(O)-, -R⁷0- - C(0)OR⁷NHC(0)NH- or -R⁷OC(0)-; R⁶ is a straight or branched alkylene of 1 to 5 carbon atoms; R⁷ is a straight or branched alkylene of 1 to 5 carbon atoms; V is -OP(0)(OR⁸)(OR⁹), -P(0)(OR⁸)(OR⁹), or -Si(L¹)_x(L²)₃-_x; v, s, and t are independently 0 or 1 ; R⁸ and R⁹ are independently H,

HN(R²)3, or straight or branched alkyls of 1 to 5 carbon atoms; L¹ and L² are independently selected from R¹⁰ or OR¹⁰; x is 0 to 3; R¹¹ is H or straight or branched alkyls of 1 to 5 carbon atoms; R¹⁰ is a straight or branched alkyi of 1 to 4 carbon atoms; Z is selected from H, Na, Li, Cs, K, HN(R²)3, a hydroxy-terminated straight or branched alkyi of 1 to 10 carbons, or a hydroxy-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units, or mixtures thereof; Y is selected from - CH2O-, -C(0)0-, -OC(O)-, -R⁵OC(0)-, -

C(0)0(CH₂CH20)m(CH2CH(CH3)0)n- or -C(0)OR⁵0-; R⁵ is a straight or branched alkylene of 1 to 10 carbons; m and n are independently integers of 0 to 20, provided that m+n>0; R³ is a straight or branched alkyl chain of 1 to 30 carbons, optionally having at least one olefinic unit, or mixtures thereof; Unit A is present in an amount of about 10 to 60 mol %; Unit B is present in an amount of about 1 to 30 mol%; Unit C is present in an amount of about 1 to 50 mol%; and Unit D is present in an amount of 0 to 40 mol%; wherein the sum of repeat units is equal to 100 mol%; and wherein the coating composition comprises (a) the coating base in an amount of from about 95 to 99.98% and (b) the polymer compound in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b).

DETAILED DESCRIPTION OF THE INVENTION

Herein trademarks are shown in upper case.

The terms "(meth)acrylic" or "(meth)acrylate" indicate, respectively, methacrylic and/or acrylic, and methacrylate and/or acrylate; and the term (meth)acrylamide indicates methacrylamide and/or acrylamide.

By the term "alkyd coating" as used hereinafter is meant a conventional liquid coating based on alkyd resins, typically a paint, clear coating, or stain. The alkyd resins are complex branched and cross-linked polyesters containing unsaturated aliphatic acid residues.

By the term "urethane coating" as used hereinafter is meant a conventional liquid coating based on Type I urethane resins, typically a paint, clear coating, or stain. Urethane coatings typically contain the reaction product of a polyisocyanate, usually toluene diisocyanate, and a polyhydric alcohol ester of drying oil acids. Urethane coatings are classified by ASTM D16 into five categories. Type I urethane coatings contain a minimum of 10% by weight of a pre-reacted autoxidizable binder, characterized by the absence of significant amounts of free isocyanate grous. These are also known as uralkyds, urethane-modified alkyds, oil-modified urethanes, urethane oils, or urethane alkyds. Type I urethane coatings are the largest volume category of polyurethane coatings and include paints, clear coatings, or stains. The cured coating for a Type I urethane coating is formed by air oxidation and polymerization of the unsaturated drying oil residue in the binder.

By the term "unsaturated polyester coating" as used hereinafter is meant a conventional liquid coating based on unsaturated polyester resins, dissolved in monomers and containing initiators and catalysts as needed, typically as a paint, clear coating, stain, or gel coat formulation.

By the term "water-dispersed coatings" as used herein is meant surface coatings intended for the decoration or protection of a substrate, comprising essentially an emulsion, latex, or suspension of a film-forming material dispersed in an aqueous phase, and optionally containing surfactants, protective colloids and thickeners, pigments and extender pigments, preservatives, fungicides, freeze-thaw stabilizers, antifoam agents, agents to control pH, coalescing aids, and other ingredients.

Water-dispersed coatings are exemplified by, but not limited to, pigmented coatings such as latex paints, unpigmented coatings such as wood sealers, stains, and finishes, coatings for masonry and cement, and water- based asphalt emulsions. For latex paints the film forming material is a latex polymer of acrylate acrylic, styrene acrylic, vinyl-acrylic, vinyl, or a mixture thereof. Such water-dispersed coating compositions are described by C. R. Martens in "Emulsion and Water-Soluble Paints and Coatings" (Reinhold Publishing Corporation, New York, NY, 1965).

By the term "coating base" as used herein is meant a liquid formulation of a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating, which is later applied to a substrate for the purpose of creating a lasting film on said surface. The coating base includes those solvents, pigments, fillers, and functional additives found in a conventional liquid coating. For example, the coating base formulation may include a polymer resin and pigment dispersed in water, where the polymer resin is an acrylic polymer latex, vinyl-acrylic polymer, vinyl polymer, Type I urethane polymer, alkyd polymer, epoxy polymer, or unsaturated polyester polymer, or mixtures thereof. The present invention comprises a composition comprising (a) a coating base selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and (b) a polymer compound comprising the repeat Units A, B, and C, and optionally Unit D in any ord

The polymer compounds comprise three or more repeating units derived from monomers from each of four groups. Monomers forming Unit A are fluorinated monomers such as perfluoroalkylalkyl (meth)acrylates; monomers forming Unit B are monomers such as (meth)acrylic

phosphates or (meth)acrylic alkoxysilanes; monomers forming Unit C are hydrophilic hydroxyalkyl (meth)acrylates, alkoxylated (meth)acrylates, or (meth)acrylic acid which are optionally neutralized to form a salt, and monomers forming Unit D are hydrophobic alkyl (meth)acrylates or fatty acid (meth)acrylates. The repeating units of the polymer compound can occur in any random, block, or other sequence in the proportions described above.

The crosslinkable polymer compound contains repeat units from at least Units A, B and C. In one embodiment, Unit A is present in an amount from about 10 to about 60 mol%; in another embodiment, Unit A is present in an amount from about 25 to about 55 mol %; and in a third embodiment, Unit A is present in an amount from about 30 to about 50 mol %. In one embodiment, Unit B is present in an amount from about 1 to about 30 mol%; in another embodiment, Unit B is present in an amount from about 1 to 20 mol%; and in a third embodiment, Unit B is present in an amount from about 1 to about 10 mol%. In one embodiment, Unit C is present in an amount of 1 to 50 mol %, and in another embodiment, Unit C is present in an amount from about 1 to about 40 mol %. In one

embodiment, Unit D is also present in the polymer composition. In this embodiment, Unit D is present in an amount of 0.1 to 40 mol %; in another embodiment, Unit D is present in an amount from about 1 to about 30 mol %; and in a third embodiment, Unit D is present in an amount from about 1 to about 20 mol %. In another embodiment, additional repeat units are also present in the polymer composition.

The polymer compound (b) must have a molecular weight high enough to provide cleanability and durability but low enough to allow the polymer molecules to migrate through the coating medium. In one embodiment, the number average molecular weight M_n is about 1500 to about 50,000 Daltons; in a second embodiment, the number average molecular weight M_n is about 5000 to about 40,000 Daltons; and in a third embodiment, the number average molecular weight M_n is about 8000 to about 35,000 Daltons. In one embodiment, the weight average molecular weight M_w is about 5000 to about 50,000 Daltons; in a second

embodiment, the weight average molecular weight M_w is about 8000 to about 30,000 Daltons; and in a third embodiment, the weight average molecular weight M_w is about 10,000 to about 20,000 Daltons. The polydispersity index (PDI) may be about 1 .0 to about 3.0; in another embodiment, about 1 .1 to about 2.0, and in a third embodiment, about 1 .2 to about 1 .9. In another embodiment, the polymer compound is a hyperbranched polymer that results from the copolymerization with a monomer with at least two ethylenic unsaturated groups. In this case, the Mw can be up to 300,000, and PDI may be up to 6.0.

Fluorinated (meth)acrylate monomers useful for forming Unit A are synthesized from the corresponding alcohols. These fluorinated

(meth)acrylate compounds are prepared by either esterification of the corresponding alcohol with (meth)acrylic acid or by transesterification with methyl (meth)acrylate. Such preparations are well-known in the art.

In one embodiment, R_f in Unit A is a straight or branched-chain perfluoroalkyl group predominately containing from 2 to 6 carbon atoms, optionally interrupted by one or more ether oxygens -0-, -CH₂- or -CFH- groups. Such interrupted Rf groups include but are not limited to

C3F7OCF2CF2, C3F7OCF2CF2OCF2CF2, C5F11 OCF2CF2, C4F9CH2CF2, C6F13CH2CF2, C3F7CFH, C5F11CFH, and similar variations. In another aspect, R_f in Unit A is a straight chain perfluoroalkyl group of 2 to 6 carbon atoms, and in another embodiment, 4 to about 6 carbon atoms. One preferred embodiment of the monomer forming Unit A is a

perfluoroalkylethyl (meth)acrylate having the formula:

F(CF₂CF₂)_qC₂H₄OC(O)-C(R)=CH₂ wherein q is 1 to about 3 or a mixture thereof, and preferably

predominately 2 to about 3 or a mixture thereof, and R is H or methyl.

Examples of suitable linking groups Q in Unit A include straight chain, branched chain or cyclic structures of alkylene, arylene, alkoxy, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, and combinations of such linking groups such as sulfonamidoalkylene. In one embodiment, Q is a straight chain alkylene of 1 to about 15 carbon atoms or -CONR'(C_rH2r)-, the (C_rH_2r) group is linear or branched, and preferably is linear. In this case, r is 1 to 14. Within moiety A and Q, the alkyl in R' is linear or branched. In one embodiment, Q is a straight or branched alkylene of 1 to 4 carbon atoms, and in a second embodiment, Q is a straight or branched alkylene of 2 to 4 carbon atoms. Mixtures of fluorinated monomers may also be used.

Suitable fluorinated alcohols capable of forming the fluorinated (meth)acrylate monomers include but are not limited to

C4F₉SO2NH(CH2)₃OH, C6Fi₃SO₂NH(CH2)3OH, C₈Fi₇SO2NH(CH2)3OH, C4F₉SO2NH(CH2)₂OH, C6Fi₃SO₂NH(CH2)2OH, C₈Fi₇SO2NH(CH2)2OH, C4F₉SO2N(CH3)(CH2)2OH, C6Fi3SO₂N(CH₃)(CH2)2OH,

C8Fi7SO2N(CH₃)(CH2)2OH, C4F₉CH2CF2SO2NH(CH2)3OH,

C₃F₇OCF2CF2SO2NH(CH2)3OH, C4F₉CH2CH2CF2CF₂SO2NH(CH2)3OH, C4F₉OCFHCH2CH₂SO2NH(CH2)3OH, C4F₉SO2CH2CH₂NH(CH2)3OH, C6Fi3SO2CH2CH₂NH(CH2)3OH, C₈Fi₇SO2CH2CH2NH(CH2)3OH,

C4F₉CH2CH2SO2NHCH2CH₂OH, C6F13CH2CH2SO2NHCH2CH2OH, C8F17CH2CH2SO2NHCH2CH2OH, C4F₉CH₂CH2SO2N(CH₃)CH2CH2OH, C6Fi3CH2CH2SO2N(CH3)CH2CH₂OH,

C8Fi7CH2CH2SO2N(CH3)CH2CH₂OH, C₄F₉(CH₂)2OH, C6Fi₃(CH₂)2OH, C₈Fi7(CH2)2OH, C₄F₉OH, CeFisOH, CsFiyOH, C4F₉CH2CH2CH₂OH, C6F13CH2CH2CH2OH, C₄F₉CH₂OH, C6F13CH2OH,

C4F₉CH2CF2CH2CH₂OH, C6F13CH2CF2CH2CH2OH, C4F9CH2CF2CH2CF2CH2CH2OH, C6F13CH2CF2CH2CF2CH2CH2OH, C3F7OCF2CF2CH2CH2OH, C2F5OCF2CF2CH2CH2OH,

CF3OCF2CF2CH2CH2OH, C3F7(OCF2CF2)2CH2CH₂OH,

C2F5(OCF2CF2)2CH2CH₂OH, CF3(OCF2CF2)2CH2CH₂OH,

C3F7OCHFCF2OCH2CH2OH, C2F5OCHFCF2OCH2CH2OH,

CF3OCHFCF2OCH2CH2CH2OH, C3F7OCHFCF2OCH2CH2CH2OH, C2F5OCHFCF2OCH2CH2CH2OH, CF3OCHFCF2OCH2CH2OH,

C4F9CH2CH2SCH2CH2OH, C6F13CH2CH2SCH2CH2OH, C4F9SCH2CH2OH, C6F13SCH2CH2OH, C4F9CH2CH2CF2CF2CH2CH2OH,

C3F70CF(CF3)C(0)NHCH2CH₂OH,

C3F70CF(CF3)C(0)N(CH3)CH2CH₂OH, C4F₉NHC(0)NHCH2CH20H, C6Fi3NHC(0)NHCH2CH₂OH, HCF2(CF2)4CH₂OH, HCF2(CF2)6CH₂OH, HCF2(CF2)8CH20H, and similar variations thereof.

Examples of monomers used to form Unit B include ethylenically unsaturated monomers having a pendant phosphate, phosphonate, or silane functional group. Such functional groups are capable of anchoring onto reactive components traditionally found in coating bases, or with additives to the coating base, such as inorganic oxides or amine compounds. In one aspect, t is 1 and R⁶ is methylene, ethylene, or propylene. In one aspect, R⁷ is methylene, ethylene, or propylene.

Specific examples of silanes include but are not limited to trialkoxysilyl alkyl (meth)acrylates such as trimethoxysilyl ethyl(meth)acrylate, trimethoxysilyl propyl(meth)acrylate, triethoxysilyl ethyl(meth)acrylate, or triethoxysilyl propyl(meth)acrylate; allyl trialkoxysilanes such as

allyltriethoxysilane, allyltrimethoxysilane, or allyltripropoxysilane; and vinyl trialkoxysilanes such as triethoxyvinylsilane or tripropoxyvinylsilane.

Versions of the previous exemplified silanes having mixtures of alkoxy groups, such as monoethoxydimethoxysilyl alkyl (meth)acrylates, and having one or two alkyl groups, such as methyldimethoxysilyl

(meth)acrylates, are also envisioned. In one aspect, at least one of L¹ or L² is OR¹⁰. Specific examples of phosphate or phosphonate monomers include but are not limited to ethylene glycol (meth)acrylate phosphate, diethyl allyl phosphate, and the compounds listed below. Variations of the compounds below, including using different alkyl or alkylene units, or interchanging OH and alkoxy, are also included.

Unit C is formed from hydrophilic monomer compounds, such as hydroxy-terminal or acidic (meth)acrylates, or mixtures thereof. Where Z is a hydroxy-terminal straight or branched alkyl, suitable examples include, but are not limited to, one or more hydroxyalkyl (meth)acrylates having alkyl chain lengths of 2 to 4 carbon atoms, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, and 3- hydroxypropyl methacrylate. In one embodiment, R² is H or alkyl radical of 1 to 2 carbon atoms. Where Unit B is formed from one or more alkoxylated (meth)acrylates or poly(alkylene glycol) (meth)acrylates, suitable monomers may contain between 1 and 40 oxyalkylene units per molecule. In another embodiment, monomers contain from 2 to 20 oxyalkylene units per molecule, and in a third embodiment, from 4 to 12 oxyalkylene units per molecule. Such monomers include but are not limited to ethyltriethyleneglycol (meth)acrylate, ethoxylated

(meth)acrylates, poly(ethylene glycol) (meth)acrylates, poly(ethylene glycol) methyl ether (meth)acrylates, propoxylated (meth)acrylates, poly(propylene glycol) (meth)acrylates, or poly(propylene glycol) methyl ether (meth)acrylates.

In one embodiment, monomers used to form Unit C are acrylic acid or methacrylic acid; and Z is H, Na, Li, Cs, K, HN(R²)3, or mixtures thereof. In one embodiment, Z is NH₄ or Na, or a mixture thereof. Where Z is not

H, Unit C is formed by neutralizing the (meth)acrylic acid unit of the copolymer with a base, including but not limited to alkali metal hydroxides, alkali metal carbonates, ammonia, alkyl amines, or alkanolamines.

Unit D provides a hydrophobic functionality, optionally having a crosslinkable olefin group. In one embodiment, R³ has at least one olefinic unit, and the monomers used to form Unit D are at least one vinylic or (meth)acrylic monomer having a straight or branched alkyl chain of 2 to 30 carbons and having 1 to 15 olefinic units. In one embodiment, the alkyl chain contains 2 to 22 carbons, and in a third embodiment, the alkyl chain contains 3 to 18 carbons. The alkyl chains may contain 1 to 15 olefinic units but in another embodiment may contain 1 to 6 olefinic units, and in a third embodiment may contain 1 to 3 olefinic units. Such monomers may be formed from the reaction of hydroxyl-terminal (meth)acrylates or allylic compounds with fatty acids. Where Y is -

C(0)0(CH₂CH20)m(CH2CH(CH₃)0)n- or -C(0)OR⁵0-, the monomer is the reaction product of an alkoxylated (meth)acrylic or vinylic alcohol with fatty acids. Fatty acids may include but are not limited to lauric acid, palmitic acid, stearic acid, capric acid, lauric acid, mysteric acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, ricinoleic acid, erucic acid, palmitoleic acid, vaccenic acid, eicosenoic acid, eladic acid, eurucicic acid, nervonic acid, pinolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexanoic acid, eicosadienoic acid, docosatetranoic acid, and mixtures thereof. Specific examples of monomers used to form Unit D include but are not limited to oleic (meth)acrylate, linoleic (meth)acrylate, palmitic methyl ester, soybean oil methyl ester, sunflower oil methyl ester, oleic ethyl (meth)acrylate, ricinoleic (meth)acrylate, erucic (meth)acrylate, palmitoleic (meth)acrylate, vaccenic (meth)acrylate, eicosenoic

(meth)acrylate, eladic (meth)acrylate, eurucicic (meth)acrylate, nervonic (meth)acrylate, pinolenic (meth)acrylate, arachidonic (meth)acrylate, eicosapentaenoic (meth)acrylate, docosahexanoic (meth)acrylate, eicosadienoic (meth)acrylate, docosatetranoic (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, palmitic (meth)acrylate, caprylic (meth)acrylate, captric (meth)acrylate, mysteric (meth)acrylate, arachidic (meth)acrylate, behenic (meth)acrylate, lignoceric (meth)acrylate, or cetyl (meth)acrylate, and versions of the same having different chain lengths.

In another embodiment, Unit D may be formed from (meth)acrylic monomers having pendant straight or branched alkyl groups of 1 to 30 carbons. In one embodiment, the alkyl groups contain 1 to 22 carbons, and in a third embodiment, the alkyl groups contain 6 to 22 carbons.

Specific examples of such monomers include but are not limited to stearyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, or cetyl (meth)acrylate.

The polymer compound may or may not further comprise additional repeat units outside of Units A, B, C, and D, resulting from the use of additional monomers. Suitable monomers are ethylenically-unsaturated monomers, including but not limited to, amine monomers such as diethylaminoethyl acrylate and/or dimethylaminoethyl methacrylate, glycidyl (meth)acrylates, aminoalkyl methacrylate hydrochloride, acrylamide, alkyl acrylamides, or n-methylol (meth)acrylamide. When no additional repeat units outside of Units A, B, C, or D are used, then the sum of A+B+C+D is equal to 100%. When additional repeat units are present, then the sum A+B+C+D+ any additional monomer repeat units is equal to 100%.

The polymer compound optionally further comprises a residue of a chain transfer agent, known as a polymerization regulator. The term "residue" is herein defined as the portion of the chain transfer agent structure that is covalently bonded to the polymer molecule. The total polymer reaction mixture may also include some polymer molecules that do not contain the chain transfer agent residue.

The chain transfer agent can be used in amounts to limit or control the molecular weight of the fluoropolymer, typically in amounts of about 1 to 25 mol%, preferably about 2 to 20 mol%, more preferably about 3 to 15 mol%, and most preferably 5 to 10 mol%, based on the total amount of chain transfer agent and monomers employed. Chain transfer agents may include hydrophobic chain transfer agents, including dodecyl mercaptans, or may an include a hydrophilic chain transfer agent. In one embodiment, the chain transfer agent has the formula (I)

wherein g is 1 or 2; D is a linear or branched alkylene of 1 to about 4 carbon atoms, optionally substituted with one or more hydrophilic functional groups selected from hydroxyl, carboxyl, or amine; and G is a hydrophilic functional group selected from hydroxyl, carboxyl, thiol, or amine. Where g=2, the chain transfer agents are disulfide compounds of the formula G-D-S-S-D-G. Suitable chain transfer agents include but are not limited to dodecanethiol, thioglycerol, mercaptoethanol, thioglycolic acid, dithioerythritol, 2-mercaptopropionic acid, and 3-mercaptopropionic acid, or mixtures thereof.

The polymer compounds in the present invention are prepared by polymerization of the fluorinated and non-fluorinated monomers. The polymerization process comprises contacting the fluorinated and non- fluorinated monomers as defined hereinabove in an organic solvent in the presence of a free radical initiator, chain transfer agent, and optionally other monomers in an inert atmosphere. For example, the monomers can be mixed in a suitable reaction vessel equipped with an agitation device. A heating source and a cooling source are provided as necessary. In a typical process, the fluorinated and non-fluorinated monomers are combined in the reaction vessel with the solvent and chain transfer agent to provide a reaction mixture, and the reaction mixture is heated to an appropriate temperature, e.g. 80 °C. Alternatively, the monomers may be fed one at a time, or in a mixture, to an existing solution in a reaction vessel at a selected feed rate. In this embodiment, the existing solution in the reaction vessel may contain the solvent; the solvent and chain transfer agent; or the solvent, chain transfer agent, and one or more monomers. In another embodiment, the chain transfer agent may be fed alone, or in a mixture with one or more monomers, to an existing solution in a reaction vessel at a selected feed rate. In this embodiment, the existing solution in the reaction vessel may contain the solvent; the solvent and one or more monomers; or the solvent, one or more monomers, and the initiator. In each embodiment, the initiator may be included in the existing solution or may be fed into the reactor at a later time.

Temperatures in the range of 20-90 °C may be suitable where organic peroxides or azo compounds are used, depending, for example, on the choice of organic solvent and the choice of free radical initiator. Temperatures of 0-50 °C are suitable where oxidation-reduction (redox) initiators are used. The free radical initiator is typically added after the reaction mixture has reached the appropriate reaction or activation temperature.

Suitable free radical initiators include organic peroxides and azo compounds. Examples of particularly useful organic peroxides are benzoyl peroxide, f-butyl peroxide, acetyl peroxide, and lauryl peroxide. Examples of particularly useful azo compounds include 2,2'-azobis(2- amidinopropane dihydrochloride, 2,2'-azobis(isobutyramidine)

dihydrochloride, and azodiisobutylronitnle. Azo initiators are commercially available from E. I. du Pont de Nemours and Company, Wilmington, DE, under the name of "VAZO".

Suitable redox initiators include potassium or ammonium

peroxydisulfate; combinations of peroxides such as hydrogen peroxide with Fe²⁺, Cr²⁺, V²⁺, Ti³⁺, Co²⁺, Cu⁺; combinations of HSOs^", SOs^2", S2O3²-, or S2O5^2" with Ag⁺, Cu²⁺, Fe³⁺' CIO^3", or H2O2; combinations of organic alcohols with Ce⁴⁺, V⁵⁺, Cr⁶⁺, or Mn³⁺; and combinations of

peroxydiphosphate compounds with Ag⁺, V⁵⁺, or Co²⁺. Such systems may be used when low temperature or rapid activation is desirable.

The free radical initiator is generally added over a period of time after the reaction monomers have dissolved in the solvent and/or after the reaction mixture is at the desired temperature. The radical initiator is added in an effective amount. By an "effective amount" of a radical initiator is meant an amount sufficient to initiate the reaction between the monomers and preferably to sustain the reaction for a sufficient period of time to maximize yield of the polymer product. An effective amount of initiator will vary with the exact composition and reaction conditions used. An effective amount of initiator for a given set of conditions is easily determined experimentally by one skilled in the art.

Suitable solvents are alkanes, alcohols and ketones having boiling points of less than 130 °C. Suitable organic solvents useful in the preparation of the fluoropolymer include methyl isobutyl ketone, butyl acetate, tetrahydrofuran, acetone, isopropanol, ethyl acetate, methylene chloride, chloroform, carbon tetrachloride, cyclohexane, hexane, dioxane, hexafluoroisopropanol, and mixtures of two or more thereof.

Cyclohexane, isopropanol, methyl isobutyl ketone, or mixtures thereof are preferred. Blends of isopropanol and methyl isobutyl ketone are particularly preferred, since both solvents form azeotropes with water boiling below 100°C, facilitating their removal from the final aqueous dispersion. Blends of organic solvents with other types of co-solvents, including water, may also be used. Preferred are isopropanol /methyl isobutyl ketone blends containing between about 20% and about 80% of methyl isobutyl ketone.

The polymer compound as described above is preferably in the form of an aqueous dispersion. After the polymerization is complete, as can be monitored by ¹ H NMR, the acidic polymer solution can be neutralized using a basic water solution to form an aqueous dipserion. The amount of base necessary is calculated by assuming complete salt formation of all acid functionalities. Optionally 0 - 5% mole percent excess of base is added to ensure conversion of all acid to salt. The final pH of the emulsion is between about 6 and about 9, and preferably is between 6 and 8. The bases suitable for the neutralization are alkali metal hydroxides, alkali metal carbonates, ammonia, alkyl amines, or

alkanolamines. Ammonia solution is preferred. Following neutralization, the organic solvents may be removed by distillation to form a completely aqueous system.

The polymer compound dispersions produced as described above may be used directly in a coating composition, or added solvent (the

"application solvent") may be added to achieve a desirable solids content. The application solvent is typically a solvent selected from the group consisting of alcohols and ketones.

The polymer compounds are useful as coatings additives, wherein the polymer compound can be added to a coating base, which is applied to a substrate. When the coating is applied to a substrate, the additive compound is allowed to first migrate to the surface and subsequently crosslink to form a durable oil-, dirt-, and water-repellent surface.

As noted above, the coating base is a liquid formulation of a water- dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating, which is later applied to a substrate for the purpose of creating a lasting film on said surface. In one embodiment, the coating base comprises a polymer which having pendant hydroxyl or carboxylic acid groups. The coating base includes those solvents, pigments, fillers, and functional additives found in a conventional liquid coating. Typically, the coating base may include a resin compound from 10 to 60% by weight, from 0.1 to 80% by weight of functional additives including pigments, fillers, and other additives, and the balance of the coating base composition is water or solvent. For an architectural coating, the resin compound is in an amount of about 30 to 60% by weight, functional additives including pigments, extenders, fillers, and other additives are in an amount of 0.1 to 60% by weight, with the balance being water or solvent. In one aspect, the coating base comprises a reactive component selected from a phosphate-reactive compound, a phosphonate-reactive compound, or an alkoxysilane-reactive compound. Such compounds may be part of the polymer resin, part of a pigment or functional additive, or may be added to the coating base for the purpose of anchoring the fluorinated polymer compound of the invention. Such reactive components include, but are not limited to, metal oxide particles, amine compounds, carbonate compounds, or Lewis base compounds.

The coating compositions may further comprise additional components to provide surface effects to the resulting coating. For example, the composition may further comprise a non-polymeric ethylenically unsaturated crosslinkable compound to provide additional crosslinking sites for the crosslinkable polymer compound. In one embodiment, this non-polymeric crosslinkable compound is (c) a fatty acid compound in an amount of about 0.001 to 1 % by weight, based on the total weight sum of coating base (a) + polymer compound (b) + fatty acid (c). Any fatty acid, including those listed above for use in forming the monomer of Unit D, may be employed. In one embodiment, the fatty acid (c) is the same fatty acid used to form the monomer of Unit D. In another embodiment, the composition further comprises an inorganic oxide particle, or the coating base further comprises an inorganic oxide particle. In another embodiment, the coating compositions further comprise a polymerization initiator, such as a photoinitiator. Such compounds aid in further crosslinking the crosslinkable polymers once migrated to the coating surface.

The coating compositions may also include a pigment. Such a pigment may be part of the coating base formulation, or may be added subsequently. Any pigment can be used with the present invention. The term "pigment" as used herein means opacifying and non-opacifying ingredients which are particulate and substantially non-volatile in use. Pigment as used herein includes ingredients labeled as pigments, but also ingredients typically labeled in the coating trade as inerts, extenders, fillers, and similar substances.

Representative pigments that can be used with the present invention include, but are not limited to, rutile and anatase T1O2, clays such as kaolin clay, asbestos, calcium carbonate, zinc oxide, chromium oxide, barium sulfate, iron oxide, tin oxide, calcium sulfate, talc, mica, silicas, dolomite, zinc sulfide, antimony oxide, zirconium dioxide, silicon dioxide, cadmium sulfide, cadmium selenide, lead chromate, zinc chromate, nickel titanate, diatomaceous earth, glass fibers, glass powders, glass spheres, MONASTAL Blue G (C. I. Pigment Blue 15), molybdate Orange (C. I. Pigment Red 104), Toluidine Red YW (C. I. Pigment 3)- process aggregated crystals, Phthalo Blue (C. I. Pigment Blue 15)- cellulose acetate dispersion, Toluidine Red (C. I. Pigment Red 3),

Watchung Red BW (C.I. Pigment Red 48), Toluidine Yellow GW (C. I.

Pigment Yellow 1 ), MONASTRAL Blue BW (C. I. Pigment Blue 15),

MONASTRAL Green BW (C. I. Pigment Green 7), Pigment Scarlet (C. I. Pigment Red 60), Auric Brown (C. I. Pigment Brown 6), MONASTRAL Green G (C.I. Pigment Green 7), MONASTRAL Maroon B, MONASTRAL Orange, and Phthalo Green GW 951.

Titanium dioxide (T1O2) is the preferred pigment to use with the present invention. Titanium dioxide pigment, useful in the present invention, can be in the rutile or anatase crystalline form. It is commonly made by either a chloride process or a sulfate process. In the chloride process, TiCU is oxidized to T1O2 particles. In the sulfate process, sulfuric acid and ore containing titanium are dissolved, and the resulting solution goes through a series of steps to yield T1O2. Both the sulfate and chloride processes are described in greater detail in "The Pigment Handbook", Vol. 1 , 2nd Ed. , John Wiley & Sons, NY (1988), the teachings of which are incorporated herein by reference.

When used as an additive to a coating base, the polymer

compound is effectively introduced to the coating base by thoroughly contacting, e.g., by mixing the fluoropolymer composition with the coating base. The contacting of polymer compound and coating base can be performed, for example and conveniently, at ambient temperature. More elaborate contacting or mixing methods can be employed such as using a mechanical shaker or providing heat. Such methods are generally not necessary and generally do not substantially improve the final coating composition. The polymer compound of the invention is generally added at about 0.02 weight % to about 5 weight % on a dry weight basis of the polymer compound to the weight of the wet paint. In one embodiment, from about 0.02 weight % to about 0.5 weight % is used, and in a third embodiment, from about 0.05 weight % to about 0.25 weight % of the polymer compound is added to the paint. The polymer compound may be added as an aqueous dispersion, aqueous emulsion, organic solvent-based dispersion or emulsion, or organic solvent-based solution. In one aspect, the polymer compound of the invention is different in composition to the polymer of the coating base resin.

b. applying the coating composition to a substrate to form a coating; and

c. allowing the polymer compound to migrate to the coating surface; wherein the polymer compound comprises the repeat Units A, B, and C, and optionally Unit D in any order; where Rf is a straight or branched-chain perfluoroalkyi group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -0-, -CH2-, -CFH-, or combinations thereof; A is O, S, or N(R²); Q is a straight chain, branched chain or cyclic structure of alkylene, alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups; R¹ is H or CH3; R² is independently selected from H or a linear or branched alkyi of 1 to about 4 carbon atoms; R⁴ is H, an alkyi of 1 to 4 carbon atoms, or -C(0)OR¹¹ ; X is -C(0)0- -C(O)-, -R⁷0- - C(0)OR⁷NHC(0)NH- or -R⁷OC(0)-; R⁶ is a straight or branched alkylene of 1 to 5 carbon atoms; R⁷ is a straight or branched alkylene of 1 to 5 carbon atoms; V is -OP(0)(OR⁸)(OR⁹), -P(0)(OR⁸)(OR⁹), or -Si(OR¹⁰)₃; v, s, and t are independently 0 or 1 , provided that t is only 0 when V is - OP(0)(OR⁸)(OR⁹), -P(0)(OR⁸)(OR⁹), or -Si(L¹)_x(L²)₃-_x; v, s, and t are independently 0 or 1 ; R⁸ and R⁹ are independently H, HN(R²)3, or straight or branched alkyls of 1 to 5 carbon atoms; L¹ and L² are independently selected from R¹⁰ or OR¹⁰; x is 0 to 3; R¹¹ is H or straight or branched alkyls of 1 to 5 carbon atoms; R¹⁰ is a straight or branched alkyl of 1 to 4 carbon atoms; Z is selected from H, Na, Li, Cs, K, HN(R²)3, a hydroxy- terminated straight or branched alkyl of 1 to 10 carbons, or a hydroxy- terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units, or mixtures thereof; Y is selected from -C H2O-, -C(0)0-, -OC(O)-, - R⁵OC(0)-, -C(0)0(CH₂CH20)m(CH2CH(CH3)0)n- or -C(0)OR⁵0-; R⁵ is a straight or branched alkylene of 1 to 10 carbons; m and n are

independently integers of 0 to 20, provided that m+n>0; R³ is a straight or branched alkyl chain of 1 to 30 carbons, optionally having at least one olefinic unit, or mixtures thereof; Unit A is present in an amount of about 10 to 60 mol %; Unit B is present in an amount of about 1 to 30 mol%; Unit C is present in an amount of about 1 to 50 mol%; and Unit D is present in an amount of 0 to 40 mol%; wherein the sum of repeat units is equal to 100 mol%; and wherein the coating composition comprises (a) the coating base in an amount of from about 95 to 99.98% and (b) the polymer compound in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b). In another aspect, the coating base further comprises a reactive component selected from a phosphate-reactive compound, phosphonate-reactive compound, or alkoxysilane-reactive compound, and the process further comprises (d) anchoring the polymer compound to the reactive component to form a durable coating. In yet another aspect, the process further comprises a step (e) of polymerizing the olefinic unit in Unit D after the polymer compound has migrated to the coating surface.

The coating compositions of the present invention are useful for providing a protective and/or decorative coating to a wide variety of substrates. Such substrates include primarily construction materials and hard surfaces. The substrate is preferably selected from the group consisting of wood, metal, wallboard, masonry, concrete, fiberboard, and paper. Other materials may also be used as the substrate. The coatings of the present invention may be used to treat a substrate by contacting the substrate with a coating composition

comprising a coating base and a polymer compound and drying or curing the coating composition on the substrate. Any method of contacting a coating composition with a substrate can be used. Such methods are well known to a person skilled in the art, such as by brush, spray, roller, doctor blade, wipe, dip, foam, liquid injection, immersion or casting. Following application of the coating to a substrate, the polymer compound having a pendant olefin group as part of Unit D may be further polymerized using any conventional means, including allowing the additive to crosslink in air by oxidative curing. Radiation curing, including UV curing, may also be employed. Cure initiators and additives may be combined with the coating compositions to improve cure efficiency.

The compositions of the present invention provide performance as well as durability to coatings. They impart unexpectedly desirable surface effects such as: increased water and oil contact angles, enhanced dirt pickup resistance, and enhanced cleanability to the coating films. For these reasons, the compositions of the present invention are particularly useful in exterior coatings and paints.

MATERIALS AND TEST METHODS

All solvents and reagents, unless otherwise indicated, were purchased from Sigma-Aldrich and used directly as supplied.

1 H, 1 H,2H,2/-/-perfluorooctyl methacrylate and 1 H, 1 /-/,2/-/,2/-/-perfluorooctyl acrylate were obtained from DuPont Chemicals & Fluoroproducts.

Molecular weight analysis was performed using a Size Exclusion

Chromatography (SEC) system [Alliance 2695™, Waters Corporation (Milford, MA)] equipped with with a differential refractive index detector, multi-angle light scattering photometer and a differential capillary viscometer ViscoStar™.

Test Methods

Dosing of Polymer Additives in Paint and Test Panel Application

Aquesous dispersions of fluoroacrylic copolymers of the present invention were added at 350 ppm fluorine levels to selected commercially available interior and exterior latex paints that were, prior to dosing, free of fluoroadditives. The sample was mixed using an overhead Cowles Blade stirrer at 600 rpm for 10 minutes. The mixture was then transferred to a glass bottle, sealed and placed on a roll mill overnight to allow uniform mixing of the fluoropolymer. The samples were then drawn down uniformly on a black Leneta Mylar® card (5.5" x 10") or Aluminium Q-panel (4" x 12") via a BYK-Gardner drawdown apparatus using 5 mL bird- applicator. The paint films were then allowed to dry at room temperature for 7 days.

Test Method 1 . Evaluation of Oil Repellency via Contact Angle

Measurement

Oil contact angle measurements were used to test for the migration of fluoroadditive to the surface of the paint film. Oil contact angle testing was performed by goniometer on 1 inch strips of Leneta panel coated with dried paint film.

A Rame-Hart Standard Automated Goniometer Model 200 employing DROP image standard software and equipped with an automated dispensing system, 250 μΙ syringe, and illuminated specimen stage assembly was used. The goniometer camera was connected through an interface to a computer, allowing the droplet to be visualized on a computer screen. The horizontal axis line and the cross line could both be independently adjusted on the computer screen using the software.

Prior to contact angle measurement, the sample was placed on the sample stage and the vertical vernier was adjusted to align the horizontal line (axis) of the eye piece coincident to the horizontal plane of the sample. The horizontal position of the stage relative to the eye piece was positioned so as to view one side of the test fluid droplet interface region at the sample interface.

To determine the contact angle of the test fluid on the sample, approximately one drop of test fluid was dispensed onto the sample using a 30 μί pipette tip and an automated dispensing system to displace a calibrated amount of the test fluid. For oil contact angle measurements, hexadecane was suitably employed. Horizontal and cross lines were adjusted via the software in case of the Model 200 after leveling the sample via stage adjustment, and the computer calculated the contact angle based upon modeling the drop appearance. The initial contact angle is the angle determined immediately after dispensing the test fluid to the sample surface. Initial contact angles above 30 degrees are indicators of effective oil repellency.

Test Method 2. Dirt Pick-up Resistance (DPR) Test for Exterior Paints

DPR testing was used to evaluate the ability of the painted panels to prevent dirt accummulation. An artificial dry dirt comprised of silica gel (38.7%), aluminum oxide powder (38.7%), black iron oxide powder (19.35%) and lamp black powder (3.22%) was used for this test. The dust components were mixed and placed on a roller for 48 hours for thorough mixing and stored in a decicator.

Exterior paint samples were drawn down to Aluminium Q-panels cut to a size of 1 .5" x 2", and four replicates of these samples were taped onto a 4" x 6" metal panel. The initial whiteness (L^* initial) of each Q-panel was measured using a Hunter Lab colorimeter. The 4" x 6" metal panel was then inserted into a 45 degree angle slot cut in a wooden block. The dust applicator containing metal mesh dispensed the dust on the panels until the panels were completely covered with dust. The excess dust was then removed by lightly tapping the mounted panels 5 times on the wooden block inside the shallow tray. The 4" x 6" panel which held the dusted panels was then clamped onto a Vortex-Genie 2 for 60 seconds to remove any remaining dust. The panel was then removed and tapped 10 times to dislodge any remaining dust. The whiteness (L^* dusted) of each 1 .5" x 2" sample was re-measured using the same colorimeter, and the difference in whiteness before and after dusting was recorded. The values were averaged. DPR is expressed in terms of ΔΙ_^* where ΔΙ_^* = (L^* initial - L^* dusted). A lower AL^* value indictes better dirt pick-up resistance.

Test Method 3. Water Wash Durability (Oil Contact Angle)

Exterior paint samples were drawn down to Aluminum Q-panels cut to a size of 1 .5" x 2", fixed at an angle of 45 °, and set to wash with running water for five minutes at a flow rate of 1 L/minute. The samples were air dried for 7 days, and oil contact angles were then measured as described in Test Method 1 . Test Method 4. Weathering (WOM) for DPR and Oil Contact Angle

Durability

Accelerated weathering of coated Q-panels was performed in an ATLAS Ci5000 Xenon Lamp Weather-o-Meter. The Xenon lamp was equipped with Type S Boro Inner and Outer Filters. Weathering cycles were performed according to D6695, cycle 2. During the weathering period, the panels were subjected to repeated 2-hour programs, which included 18 minutes of light and water spray followed by 102 minutes of light only. During the entire program, panels were held at 63 °C and during the UV only segment relative humidity was held at 50%.

For a 24-hour WOM program, freshly coated aluminum Q-panels were allowed to air dry for 7-days. The initial whiteness (L^* initial) of each Q-panel was measured using a Hunter Lab colorimeter. One set of panels was subjected to DPR testing (as per Test Method 2) as well as oil and water contact angle testing (as per Test Method 1 ). A duplicate set of panels was placed in the weather-o-meter and allowed to proceed through 12 continuous 2-hour cycles according to the description above. After completion of the weathering cycles, the panels were dried, evaluated according to Test Methods 1 and 2, and re-subjected to DPR.

Examples

Preparation of Monomer A: Diethyl(methacryloyloxy)methyl phosphonate

CH2=C(CH3)CO2CH2P(O)(OCH₂CH3)2 A solution of diethyl-a-hydroxymethylphosphonate (10.0 g, 59.5 mmol) and methacrylic acid (5.12 g, 59.5 mmol) in chloroform (30 mL) was formed and maintained at 0 °C under N2. To this solution was added 1 - [(3-dimethylamino)propyl-3-ethylcarbodiimide hydrochloride (1 1 .4 g, 59.5 mmol) and 4-(dimethylamino)pyridine (0.72 g, 5.95 mmol). The solution was vigorously stirred at room temperature for 3 hours. The reaction mixture was diluted with chloroform (30 mL), washed with water (2 x 50 mL), 5% HCI (1 x 30 mL), saturated NaHCOs (1 x 30 mL), and brine (1 x 50 mL). The organic layer was dried and evaporated under vacuum to provide diethyl methacryloyloxymethylphosphonate monomer (12.9 g, 54.6 mmol). ¹ H NMR (CDC ): 5 6.1 (m, 1 H), 5.57 (m, 1 H), 4.38 (d, 1 1.0 Hz, 2H), 4.10 (q, J = 7.2 Hz, 2H), 4.12 (q, J = 7.2 Hz, 2H), 1.90 (dd, J = 1 .5, 1 .0 Hz, 3H), 1.29 (t, J = 7.2 Hz, 6H), 1 .27 (t, J = 7.2 Hz, 6H).

Preparation of Monomer B: Diethyl(methacrylamido)methyl phosphonate monomer

CH2=C(CH₃)C(0)NHCH2P(0)(OCH2CH₃)2

Hydrazine hydrate (3.0 g, 60.0 mmol) was added to a solution of diethyl(phthalimidomethyl)phosphonate (16.05 g, 54.0 mmol) in absolute ethanol (200 mL) at room temperature. The mixture was stirred for 12 hours, and a white precipitate was formed. The slurry was heated to reflux for 3 hours, cooled to room temperature, and then to 0 °C. The white solid was filtered and washed with CH2CI2 (1 x 20 mL). Evaporation of the clear filtrate provided diethyl-a-aminomethylphosphonate (8.8 g, 37.4 mmol) as a yellow oil. ¹H NMR (CDC ): δ 4.10 (m, 4H), 2.98 (d, J = 8.0 Hz, 2H), 1 .32 (t, J = 8.0 Hz, 6H).

A solution of diethyl-a-aminomethylphosphonate (2.5 g, 15.0 mmol) and methacrylic acid (1 .29 g, 15.0 mmol) in chloroform (10 mL) was formed and maintained at 0 °C under N2. To this solution was added 1 -[(3- dimethylamino)propyl-3-ethylcarbodiimide hydrochloride (2.87 g, 15.0 mmol) and 4-(dimethylamino)pyridine (0.18 g, 1.5 mmol). The solution was vigorously stirred at room temperature for 3 hours. The reaction mixture was diluted with chloroform (10 mL), washed with water (2 x 50 mL), 5% HCI (1 x 10 mL), sat. NaHCOs (1 x 10 mL) and brine (1 x 20 mL). The organic layer dried and evaporated under vacuum to provide

diethyl(methacryloylamido)methyl phosphonate monomer (2.8 g, 1 1 .9 mmol). ¹ H NMR (CDCb): δ 6.26 (bs, 1 H), 5.66 (m, 1 H), 5.30 (m, 1 H), 4.08 (q, J = 7.2 Hz, 2H), 4.10 (q, J = 7.2 Hz, 2H), 4.08 (q, J = 7.2 Hz, 2H), 4.09 (q, J = 7.2 Hz, 2H), 3.71 (dd, J = 12.0, 6.0 Hz, 2H), 1 .89 (dd, J = 1 .5, 1 .0 Hz, 3H), 1 .28 (t, J = 7.2 Hz, 6H).

Preparation of Monomer C:

CH2=C(CH3)C02CH2CH2NHCOOCH2P(Q)(OCH2CH3)2

A solution of diethyl-a-hydroxymethylphosphonate (10.0 g, 59.5 mmol) in dichlormethane (20 mL) was formed and maintained at 0 °C under N2. 2-lsocyanatoethylmethacrylate (9.22 g, 59.5 mmol) was added dropwise. The solution was vigorously stirred at room temperature for 12 hours. At the end of the reaction period, the solvents were removed under vacuum to obtain pure urethane acrylate phosphonate monomer (18.5 mmol, 57.2 mmol) as an oil. ¹H NMR (CDC ): δ 6.05 (m, 1 H), 5.53 (m, 1 H), 5.26 (bs, 1 H), 4.30 (d, 16.0 Hz, 2H), 4.17 (t, J = 6.8 Hz, 2H), 4.12 (q, J = 7.2 Hz, 2H), 4.1 1 (q, J = 7.2 Hz, 2H), 3.83 (q, J = 6.4 Hz, 2H), 1 .90 (dd, J = 1 .5, 1 .0 Hz, 3H), 1 .20 (t, J = 7.2 Hz, 6H).

Example 1

A 250 ml_ three-necked round bottom flask was equipped with a reflux condenser, a nitrogen sparge line, a TEFLON-coated magnetic stir bar, and a dip-tube for measurement of the internal temperature via a thermocouple. The flask was charged with methyl isobutylketone (MIBK, 1 1 ml_) and isopropanol (IPA, 25 ml_). The solution was subjected to subsurface sparging with N2 for 1 hour at room temperature.

A separate 100 ml flask, equipped with a rubber septum and nitrogen inlet, was charged with 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctyl methacrylate (14.58 g, 33.8 mmol), Monomer A (3.44 g, 15.48 mmol) and methacrylic acid, (3.16 g, 36.74 mmol). The solution was subjected to sub-surface sparging with N2 for 1 hour at room temperature. The monomer solution was diluted to a total volume of 20 ml_ using the MIBK/IPA from the first flask. A solution of VAZO 67 (0.395 g, 2.05 mmol) was prepared using sparged MIBK/IPA (19 ml_) from the first reaction flask.

1 -Thioglycerol (0.84 g, 7.76 mmol) was added to the first reaction flask containing the remaining sparged MIBK/IPAsolvent. The reactor was heated to 80 °C. When reaction temperature reached 80 °C, the monomer and initiator solutions were separately added over 6 hours via syringe pump. The reaction was allowed to stir for an additional 16 hours at 80 °C. Monomer consumption was monitored via ¹H NMR using mesitylene as an internal standard (97% conversion). The polymer sample was also analyzed by GPC (M_n = 4.5 kDa and PDI = 1 .6).

The polymer solution in MIBK/IPA was heated back to 70 °C. A neutralization solution consisting of NH₄OH (2.85 g, 47.0 mmol) in H2O (58.3 ml_) was prepared and heated to 45 °C. The ammonia solution was added dropwise to the polymer solution via addition funnel over 20 minutes to achieve a cloudy solution. The solution was stirred at 70 °C for an additional 1 hour and the MIBK/IPA was removed under vacuum to produce 98.3 g of a hazy yellow dispersion of polymer in water with a pH 7.5. The dispersion was determined to be 23.0 wt % solids. A calculated amount of this polymer dispersion (350 ppm of F) was added to samples of exterior test paint and evaluated as per the test methods described. Example 2

A 100 mL three-necked RB flask was equipped with a reflux condenser, a nitrogen sparge line, and a TEFLON-coated magnetic stir bar, and the flask was charged with tetrahydrofuran (THF, 28 mL) followed by 1 H, 1 /-/,2/-/,2/-/-perfluorooctyl methacrylate (10.0 g, 23.1 mmol),

Monomer B (2.35 g, 10.0 mmol), methacrylic acid, (2.5 g, 29.0 mmol) and thioglycerol (0.59 g, 5.46 mmol). The solution was subjected to subsurface sparging with N2 for 1 hour at room temperature. The reaction was heated to 60 °C and a solution of VAZO 67 (0.25 g, 1 .3 mmol) in 1 mL of N2 sparged THF was added. The reactor was heated to 70 °C for 16 hours. Monomer consumption was monitored via NMR using mesitylene as an internal standard (93% conversion). The polymer sample was also analyzed by GPC (Mn = 12.6 kDa and PDI = 1 .4).

A neutralization solution consisting of NH₄OH (2.1 1 g, 34.8 mmol) in H2O (39 mL) was heated to 45 °C and added via addition funnel to the polymer solution kept at 50 °C over 20 minutes to achieve a cloudy solution. The solution was stirred at 60 °C for an additional 60 minutes. Solvent evaporation under reduced pressure provided a cloudy dispersion of polymer additive in water (51 .3 g). A portion of the dispersion was lyophilized for further analysis and determined to be 23.0 wt % solids. A calculated amount of this polymer dispersion (350 ppm of F) was added to samples of exterior and interior test paints and evaluated as per the test methods described.

Example 3

By following a similar procedure as described in Example 1 , semi- batch polymerization was performend with 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctyl methacrylate (14.58 g, 33.8 mmol), Monomer C (3.44 g, 10.65 mmol), and methacrylic acid (3.16 g, 36.74 mmol) using a 6-hour feed of VAZO 67 (0.395 g, 2.05 mmol) initiator and thioglycerol (0.84 g, 7.76 mmol) in MIBK/IPA. The polymer solution had >93 % monomer conversion, M_n of 5.3 kDa and PDI of 1 .5.

Neutralization of the polymer using NH₄OH (2.85 g, 47.0 mmol), in H2O (58.3 g) followed by removal of the organic solvents under vacuum provided a cloudy dispersion (23.2 wt.% solids, pH 8.0) in water. A calculated amount of this polymer dispersion (350 ppm of F) was added to samples of exterior test paint and evaluated as per the test methods described.

Example 4

By following a similar procedure as described in Example 1 , semi- batch polymerization was performend using 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctyl methacrylate (16.71 g, 38.69 mmol), phosphoric acid 2-hydroxyethyl methacrylate ester (1 .96 g, 8.6 mmol), and methacrylic acid (3.16 g, 36.74 mmol ) using a 6-hour feed of VAZO 67 (0.395 g, 2.05 mmol) initiator and thioglycerol (0.99 g, 9.1 mmol) in MIBK/IPA. The polymer solution had >79 % monomer conversion.

Neutralization of the polymer using NH₄OH (2.25 g, 37.0 mmol), in H2O (58.3 g) followed by removal of the organic solvents under vacuum provided a cloudy dispersion (28.2 wt.% solids, pH 8.5) in water. A calculated amount of this polymer dispersion (350 ppm of F) was added to samples of exterior test paint and evaluated as per the test methods described.

Example 5

By following a similar procedure as described in Example 1 , semi- batch polymerization was performed using 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctyl methacrylate (16.71 g, 38.69 mmol), phosphoric acid 2-hydroxyethyl methacrylate ester (1 .96 g, 8.60 mmol), stearyl methacrylate (2.91 g, 8.60 mmol) and methacrylic acid (2.59 g, 30.1 mmol ) using a 6-hour feed of VAZO 67 (0.395 g, 2.05 mmol) initiator and thioglycerol (0.99 g, 9.1 mmol) in MIBK/IPA. The polymer solution had >99 % monomer conversion.

Neutralization of the polymer using NH₄OH (2.37 g, 39.0 mmol), in H2O (58.3 g) followed by removal of the organic solvents under vacuum provided a cloudy dispersion (21 .7 wt.% solids, pH 8.3) in water. A calculated amount of this polymer dispersion (350 ppm of F) was added to samples of exterior test paint and evaluated as per the test methods described.

Example 6

By following a similar procedure as described in Example 1 , semi- batch polymerization was performed using 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctyl methacrylate (14.58 g, 33.75 mmol), monoacryloxyethyl phosphate (3.04 g, 15.48 mmol) and methacrylic acid (3.16 g, 36.74 mmol ) using a 6-hour feed of VAZO 67 (0.395 g, 2.05 mmol) initiator and thioglycerol (0.99 g, 9.1 mmol) in MIBK/IPA. The polymer solution had >91 % monomer conversion, M_n of 1 1 .9 kDa and PDI of 1 .7.

Neutralization of the polymer using NH₄OH (2.25 g, 37.0 mmol), in H2O (58.3 g) followed by removal of the organic solvents under vacuum provided a cloudy dispersion (32 wt.% solids, pH 7.6) in water. A calculated amount of this polymer dispersion (350 ppm of F) was added to samples of exterior test paint and evaluated as per the test methods described.

Example 7

By following a similar procedure as described in Example 1 , semi- batch polymerization was performed using 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctyl methacrylate (14.85 g, 34.39 mmol), 3-(trimethoxysilyl)propyl methacrylate (6.40 g, 25.79 mmol), and 2-hydroxyethyl methacrylate (3.36 g, 25.79 mmol ) using a 6-hour feed of VAZO 67 (0.395 g, 2.05 mmol) initiator and thioglycerol (1 .20 g, 1 1 .21 mmol) in MIBK/IPA. The polymer solution had >92 % monomer conversion. A portion of the polymer solution was dried under high vacuum and calculated to be 49.9 wt% solids. A calculated amount of this polymer dispersion (350 ppm of F) was added to samples of exterior test paint and evaluated as per the test methods described. Example 8

By following a similar procedure as described in Example 1 , semi- batch polymerization was performed using 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctyl methacrylate (14.58 g, 33.75 mmol), 3-(trimethoxysilyl)propyl methacrylate (3.84 g, 15.48 mmol), and methacrylic acid (3.16 g, 36.74 mmol ) using a 6-hour feed of VAZO 67 (0.395 g, 2.05 mmol) initiator and thioglycerol (0.99 g, 9.1 mmol) in MIBK/IPA. The polymer solution had >91 % monomer conversion.

Neutralization of the polymer using NH₄OH (2.25 g, 37.0 mmol), in H2O (58.3 g) followed by removal of the organic solvents under vacuum provided a cloudy dispersion (15.3 wt.% solids, pH 8.5) in water. A calculated amount of this polymer dispersion (350 ppm of F) was added to samples of exterior test paint and evaluated as per the test methods described. Comparative Example A

By following a similar procedure as described in Example 1 , semi- batch polymerization was performed using 1 H, 1 H,2H,2H-perfluorooctyl methacrylate (14.58 g, 33.8 mmol), hydroxyethyl methacrylate (2.51 g, 19.3 mmol), methacrylic acid (2.67 g, 31.0 mmol), VAZO 67 (0.395 g, 2.05 mmol), and 1 -thioglycerol (0.840 g, 7.76 mmol) chain transfer agent, yielding a polymer solution with >95 % monomer conversion (¹H NMR). The polymer sample was analyzed by GPC for number average molecular weight, M_n = 5.7 kDa and PDI = 1.95.

Neutralization of the polymer using NH₄OH (2.39 g, 39.4 mmol) in H2O (58.3 g), followed by removal of the organic solvents under vacuum, provided a hazy yellow dispersion (90.5 g, 21 .7 wt.% solids, pH 9) in water. A calculated amount of this polymer dispersion (350 ppm of F) was added to samples of exterior test paint and the drawdown panels evaluated as per the test methods described.

Comparative Example B

Samples of exterior test paint, without additive, were applied to drawdown panels and evaluated as per the test methods described.

Table 1 . Oil Contact Angle and Dirt Pickup Resistance Performance

Dirt Pickup

Oil Contact Angle * Resistance^**

Water After After

Example Initial Wash WOM Initial WOM

1 68 67 43 3.1 4.2

2 69 63 37 2.9 3.4

3 75 69 33 0.95 3.4

4 65 62 33 1 .9 2.6

5 65 62 43 2.2 2.6

6 66 59 42 3.5 3.6

7 69 64 35 2.8 2.1

8 62 51 28 4.8 3.6

A 73 56 20 1 .5 2.7

B 0 0 0 8.5 10.2

^*A higher value indicates better contact angle performance.

^**A lower value indicates better DPR performance. Polymers containing anchoring functionalities (Examples 1 -9) showed excellent oil contact angle retention upon water wash and WOM durability evaluation in camparison to Comparative Examples A and B, where anchoring moieties are absent. They also showed good DPR, comparable to Comparative Example A and markedly better than Comparative Example B after WOM.

Claims

CLAIMS What is claimed is:

1 . A composition comprising (a) a coating base selected from a water- dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and (b) a polymer compound comprising the repeat Units A, B, and C, and optionally Unit D in any order:

Unit A Unit B Unit C Unit D where

Rf is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -0- , -CH2-, -CFH-, or combinations thereof;

A is 0, S, or N(R²);

Q is a straight chain, branched chain or cyclic structure of alkylene, alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups;

R¹ is H or CH₃;

R² is independently selected from H or a linear or branched alkyl of

1 to about 4 carbon atoms;

R⁴ is H, an alkyl of 1 to 4 carbon atoms, or -C(0)OR¹¹ ;

X is -C(0)0-, -C(O)-, -R⁷0-, -C(0)OR⁷NHC(0)NH-, or -R⁷OC(0)-;

R⁶ is a straight or branched alkylene of 1 to 5 carbon atoms;

R⁷ is a straight or branched alkylene of 1 to 5 carbon atoms;

V is -OP(0)(OR⁸)(OR⁹), -P(0)(OR⁸)(OR⁹), or -Si(L¹)_x(L²)₃-_x;

v, s, and t are independently 0 or 1 ;

R⁸ and R⁹ are independently H, HN(R²)3, or straight or branched alkyls of 1 to 5 carbon atoms; L¹ and L² are independently selected from R¹⁰ or OR¹⁰;

x is 0 to 3;

R¹¹ is H or straight or branched alkyls of 1 to 5 carbon atoms;

R¹⁰ is a straight or branched alkyl of 1 to 4 carbon atoms;

Z is selected from H, Na, Li, Cs, K, HN(R²)3, a hydroxy-terminated straight or branched alkyl of 1 to 10 carbons, or a hydroxy-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units, or mixtures thereof;

Y is selected from -CH2O-, -C(0)0-, -OC(O)-, -R⁵OC(0)-, - C(0)0(CH2CH20)m(CH2CH(CH₃)0)n- or -C(0)OR⁵0-;

R⁵ is a straight or branched alkylene of 1 to 10 carbons;

m and n are independently integers of 0 to 20, provided that m+n>0;

R³ is a straight or branched alkyl chain of 1 to 30 carbons, optionally having at least one olefinic unit, or mixtures thereof;

Unit A is present in an amount of about 10 to 60 mol %;

Unit B is present in an amount of about 1 to 30 mol%;

Unit C is present in an amount of about 1 to 50 mol%; and

Unit D is present in an amount of 0 to 40 mol%;

wherein the sum of repeat units is equal to 100 mol%; and

wherein the composition comprises (a) the coating base in an amount of from about 95 to 99.98% and (b) the polymer compound in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b).

2. The composition of claim 1 , where the polymer compound has a number average molecular weight M_n of about 1500 to about 50,000 Daltons.

3. The composition of claim 1 , where Unit D is present in an amount of about 1 to 30 mol%.

4. The composition of claim 3, where R³ has at least one olefinic unit.

5. The composition of claim 1 , where Rf is a straight perfluoroalkyl group of 2 to 6 carbon atoms.

6. The composition of claim 1 , where the coating base comprises a reactive component selected from a phosphate-reactive compound, phosphonate-reactive compound, or alkoxysilane-reactive compound.

7. The composition of claim 6, where the reactive component is a metal oxide particle.

8. The composition of claim 1 , where the polymer compound further comprises a residue from a hydrophilic chain transfer agent of formula (I)

wherein

g is 1 or 2;

D is a linear or branched alkylene of 1 to about 4 carbon atoms, optionally substituted with one or more hydrophilic functional groups selected from hydroxyl, carboxyl, or amine; and

G is a hydrophilic functional group selected from hydroxyl, carboxyl, thiol, or amine.

9. The composition of claim 1 , where the coating base is a water- dispersed coating selected from an aqueous acrylic latex paint.

10. The composition of claim 1 , where the coating base comprises an additive selected from T1O2, clays, asbestos, calcium carbonate, zinc oxide, chromium oxide, barium sulfate, iron oxide, tin oxide, calcium sulfate, talc, mica, silicas, dolomite, zinc sulfide, antimony oxide, zirconium dioxide, silicon dioxide, cadmium sulfide, cadmium selenide, lead chromate, zinc chromate, nickel titanate, diatomaceous earth, glass fibers, glass powders, glass spheres, blue pigments, red pigments, yellow pigments, orange pigments, process aggregated crystals, brown pigments, or green pigments.

1 1 . A process for forming a coating with improved cleanability comprising

b. applying the coating composition to a substrate to form a coating; and

c. allowing the polymer compound to migrate to the coating surface;

wherein the polymer compound comprises the repeat Units A, B, and C, and optionall any order:

Unit A Unit B Unit C Unit D where

Rf is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more -0-, -CH2-, -CFH-, or combinations thereof;

A is 0, S, or N(R²);

R¹ is H or CH₃;

R² is independently selected from H or a linear or branched alkyl of 1 to about 4 carbon atoms;

R⁴ is H, an alkyl of 1 to 4 carbon atoms, or -C(0)OR¹¹ ;

X is -C(0)0-, -C(O)-, -R⁷0-, -C(0)OR⁷NHC(0)NH-, or -R⁷OC(0)-; R⁶ is a straight or branched alkylene of 1 to 5 carbon atoms;

R⁷ is a straight or branched alkylene of 1 to 5 carbon atoms; V is -OP(0)(OR⁸)(OR⁹), -P(0)(OR⁸)(OR⁹), or -Si(L¹)_x(L²)₃-_x; v, s, and t are independently 0 or 1 ;

R⁸ and R⁹ are independently H, HN(R²)3, or straight or branched alkyls of 1 to 5 carbon atoms;

L¹ and L² are independently selected from R¹⁰ or OR¹⁰;

x is 0 to 3;

R¹¹ is H or straight or branched alkyls of 1 to 5 carbon atoms;

R¹⁰ is a straight or branched alkyl of 1 to 4 carbon atoms;

R⁵ is a straight or branched alkylene of 1 to 10 carbons;

m and n are independently integers of 0 to 20, provided that m+n>0;

Unit A is present in an amount of about 10 to 60 mol %;

Unit B is present in an amount of about 1 to 30 mol%;

Unit C is present in an amount of about 1 to 50 mol%; and

Unit D is present in an amount of 0 to 40 mol%;

wherein the sum of repeat units is equal to 100 mol%; and

wherein the coating composition comprises (a) the coating base in an amount of from about 95 to 99.98% and (b) the polymer compound in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b).

12. The process of claim 1 1 , where the polymer compound has a number average molecular weight M_n of about 1500 to about 50,000 Daltons.

13. The process of claim 1 1 , where the coating base further comprises a reactive component selected from a phosphate-reactive compound, phosphonate-reactive compound, or alkoxysilane-reactive compound, and the process further comprises (d) anchoring the polymer compound to the reactive component to form a durable coating.

14. The process of claim 13, where the reactive component is a metal oxide particle.

15. The process of claim 1 1 , where Unit D is present, and R³ has at least one olefinic unit.

16. The process of claim 15, where the process further comprises a step (e) of polymerizing the olefinic unit in Unit D after the polymer compound has migrated to the coating surface.

17. A coated substrate made by the process of claim 1 1 .

18. The coated substrate of claim 17, where the substrate is selected from the group consisting of wood, metal, wallboard, masonry, concrete, fiberboard, and paper.