WO2010071887A1 - Coating compositions with improved fluorosurfactants - Google Patents

Abstract

A coating composition comprising a curable component, and a fluorine-containing compound that is non-reactive with the curable component; where the fluorine-containing compound is a polyether ester defined by the formula (I): where R includes a monovalent organic group and α is a polyether including at least one pendant alkoxy fluoroalkyl group.

Description

COATING COMPOSITIONS WITH IMPROVED FLUOROSURFACTANTS

[0001] This application gains the benefit of United States Provisional Patent Application Serial No. 61/139,219, filed on December 19, 2008, which is incorporated herein by reference.

FIELD OF THE INVENTION

[0002] Embodiments of this invention relate to coating compositions that include non-reactive fluorosurfactants. In one or more embodiments, these fluorosurfactants include polyether esters containing pendant alkoxy fluoroalkyl groups.

BACKGROUND OF THE INVENTION

[0003] In general, coatings are compositons that applied to the surface of an object or substrate to improve the characteristics thereof. For example, coating can be used to improve the appearance, adhesion, wetability, corrosion resistance, wear resistance, weather resistance, and scratch resistance of the surface. Coating compositions are often applied as a liquid to form a film on the surface of the substrate. The coating composition then cures to form a finished coating. The curing can take by several mechanisms or a combination thereof. For example, some coatings simply cure (or dry) by evaporation of a solvent to leave a finished coating. In other situations, a chemical reaction occurs whereby the constituents of the coating composition react to form a cured (which may be referred to as a cross-linked coating). This reaction may take place together with the evaporation of a solvent.

[0004] Surfactants may be added to the coating composition to improve the properties of the uncured (often referred to as wet) film, which improvements may contribute to improved properties in the cured coating. For example, it is common to add surfactants to improve the wetting, flow and leveling of coating compositions. [0005] The compounds and materials employed as surfactants in coating compositions are often complex molecules that can be difficult and/expensive to produce. For this and other reasons, there is desire to include less surfactant into coating compositions with sacrificing the benefits imparted by the surfactant onto the coating compositions.

SUMMARY OF THE INVENTION

[0006] One or more embodiments of the present invention provide a coating composition comprising a curable component, and a fluorine-containing compound that is non-reactive with the curable component; where the fluorine-containing compound is a polyether ester defined by the formula:

O

R-C-O — α where R includes a monovalent organic group and α is a polyether including at least one pendant alkoxy fluoroalkyl group.

[0007] Still other embodiments of the present invention provide a coating composition comprising a curable component, and a fluorine-containing compound, where the fluorine-containing compound is prepared by a method comprising providing an initiator compound including at least one hydroxyl group, initiating the polymerization of cyclic ether monomers with the initiator compound, where the monomers include one or more monomer having a pendant alkoxyfluoroalkyl group to provide a polyether precursor compound, and reacting the polyether precursor compound with an acid anhydride.

[0008] Still other embodiments of the present invention provide a coating composition comprising a curable component, and a fluorine-containing compound, where the fluorine-containing compound is prepared by method comprising providing a polyether having a pendant alkoxyfluoroalkyl group, and reacting the polyether with an acid anhydride.

[0009] Still other embodiments of the present invention provide a curable film formed from a coating composition, the coating composition including a curable component, and a fluorine-containing compound that is non-reactive with the curable component, where the fluorine-containing compound is a polyether ester defined by the formula:

O

R-C-O — α where R includes a monovalent organic group and α is a polyether including at least one pendant alkoxy fluoroalkyl group.

[0010] Still other embodiments of the present invention provide a cured coating including a polyether ester defined by the formula:

O

R-C-O — α where R includes a monovalent organic group and α is a polyether including at least one pendant alkoxy fluoroalkyl group, where the cured coating includes a cross-linked component and where the polyether ester is not chemically bound to the cross-linked component.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS [0011] Embodiments of the present invention are based, at least in part, on the discovery that useful curable coating compositions can be prepared by including a non- reactive fluorine-containing compound into the composition. These non-reactive compounds may be referred to as non-reactive fluorosurfactants or non-reactive fluorinated compounds. In one or more embodiments, the non-reactive fluorinated compound includes one or more alkoxy fluoro alkyl groups. In particular embodiments, the non-curing fluorinated compound is or includes a poyether and one or more alkoxy fluoroalkyl groups pendant to the polyether. In one or more embodiments, the inclusion of the non-reactive fluorinated compound into the curable coating unexpectedly yields advantageous wetting, flow and/or leveling to the coating composition. It is believed that by being non-reactive, the fluorinated compound can more readily migrate to the interfaces where high surface tensions exist. -A-

[0012] Embodiments of the invention are not limited by the type of curable coating composition in which the non-curing fluorinated compound is included. In one or more embodiments, these curable coating compositions include those reactive compositions that cure or crosslink with or in the presence of a hydroxyl group, a carboxyl group, or other active hydrogen. Examples of coating compositions of this invention include polyurethane coating composition, polyester coating composition, amino-resin coating compositions, and epoxy coating compositions.

[0013] In one or more embodiments, polyester coating compositions include alkyd coating compositions, which include a polyol, an anhydride, and a dicarboxylic acid. In one or more embodiments, alkyd resins include drying and nondrying compositions. Examples of anhydrides include, but are not limited to, phthalic anhydride and maleic anhydride. Examples of polyols include trimethylolpropane, glycerine, and pentaerythritol. In one or more embodiments, the drying resins may include triglycerides derived from polyunsaturated fatty acids (often derived from plant and vegetable oils such as linseed oil) . These coating composition may include catalysts such as metal salts, which are often referred to as driers. These catalysts may include organic salts of lead, zirconium, zinc, calcium, iron and cobalt.

[0014] In one or more embodiments, polyurethane coating compositions include isocyantes that can react to form a polymer having urethane linkages, which may also be referred to as carbamate linkages. These compositions include both moisture-curable compositions and multi-part compositions. The moisture curable compositions, which may also be referred to as "one-shot" compositions include isoyanate monomer or isocyante prepolymers can cure or crosslink by reacting with moisture in the air. Multipart compositions, which are often referred to as "two-part" compositions, may include multi-functional isocyante monomers or prepolymers and multifunctional polyols that react through a step-growth polymerization. These coating compositions may include a catalyst that can promote the formation of the carbamate linkage. Useful isocyante monomers include, but are not limited to, aromatic isocyantes such as diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI), as well as aliphatic isocyanates such as hexamethylene diisocyante (HDI) or isophorone diisocyante (IPDI) . In these or other embodiments, isocyanate prepolymers may be used. Useful hydroxyl-containing compounds include, but are not limited to, polyols such as diols or higher-order hydroxyl compounds such as triols and tetra-ols. In one or more embodiments, the polyols may include base-catalyzed polyols such as polyalkylene oxides. In these or other embodiments, the polyols may include polyesters polyols. In yet other embodiments, polyalkylene oxide-extended polyesters may be employed.

[0015] In one or more embodiments, curable amino-resin coating compositions include an amino resin and a polyester, such as alkyd resins, that can react with an amino resin. These coating compositions are disclosed in U.S. Pat. Publ. 2005/0048213, which is incorporated herein by reference. Examples of amino resins include, but are not limited to, alkylated benzoguanamine-formaldehyde, alkylated urea-formaldehyde, or alkylated melamine-formadehyde resins.

[0016] The fluorosurfactant employed in practicing the present invention is a fluorine-containing compound that is non-reactive. The non-reactive nature of the fluorosurfactant refers to the fact that the fluorosurfactant will not chemically react with the curable components of the coating composition and thereby become chemically bound or incorporated in the cross-linked network of the cured coating composition. In one or more embodiments, the non-reactive fluorosurfactant is a polyether ester having one or more pendant alkoxy fluoroalkyl groups.

[0017] In one or more embodiments, the polyether esters may be defined by the formula

O

R-C-O- α where R includes a monovalent organic group and α is a polyether including at least one pendant alkoxy fluoroalkyl group. In particular embodiments, where R is relatively inactive (e.g., an ethyl group), the polyether esters are useful as flow and level agents or as surfactants in those compositions where a protic hydrogen (e.g., — OH) may be undesirable.

[0018] In one or more embodiments, the monovalent organic groups may include hydrocarbyl groups or substituted hydrocarbyl groups such as, but not limited to alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, allyl, substituted aryl, aralkyl, alkaryl, and alkynyl groups, with each group preferably containing from 1 carbon atom, or the appropriate minimum number of carbon atoms to form the group, up to 20 carbon atoms. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, boron, oxygen, silicon, sulfur, and phosphorus atoms.

[0019] In one or more embodiments, the polyether segment includes one or more repeat units defined by the formula:

R² O R³ R_f

-R² C R² O-

R¹ where R¹ is a monovalent organic group or a substituent defined by the formula — R2 — O — R³ — Rf, R² is a divalent organic group, R³ is a divalent organic group or a bond, and Rf is a monovalent organic group with at least 25% of the hydrogen atoms being replaced by fluorine. In one or more embodiment, at least 50%, in other embodiments at least 75%, in other embodiments at least 90%, and in other embodiments at least 99% of the hydrogen atoms of the Rf group are replaced by fluorine (or in other embodiments fluorine and a complementary halogen atom) . In one or more embodiments, Rf is perfluorinated.

[0020] In one or more embodiments, the divalent organic group may include a hydrocarbylene group or substituted hydrocarbylene group such as, but not limited to, alkylene, cycloalkylene, substituted alkylene, substituted cycloalkylene, alkenylene, cycloalkenylene, substituted alkenylene, substituted cycloalkenylene, arylene, and substituted arylene groups, with each group preferably containing from 1 carbon atom, or the appropriate minimum number of carbon atoms to form the group, up to about 20 carbon atoms. Substituted hydrocarbylene group includes a hydrocarbylene group in which one or more hydrogen atoms have been replaced by a substituent such as an alkyl group. The divalent organic groups may also contain one or more heteroatoms such as, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms. [0021] In one or more embodiments, the polyether segment or tail includes one or more repeat units defined by one or more of the formulae:

or

(CH₂)_m-0 (CH₂)_n R_f where m is an integer from 1 to about 3, n is an integer from about O to 3, Rl is a hydrogen atom or monovalent organic group, and Rf is a linear or branched alkyl group including 1 to about 20 carbon atoms with at least 25% of the hydrogen atoms being replaced by fluorine. In one or more embodiments, RI is selected from hydrogen, methyl, or ethyl. In other embodiments, Rl is selected from hydrogen and methyl. In one or more embodiments, the remaining hydrogen atoms within said Rf group may optionally be replaced by other halogen atoms such as iodine, chlorine, or bromine. In one or more embodiments, the Rf group includes from 1 to 7 carbon atoms. In one or more embodiments, at least 50%, in other embodiments at least 75%, in other embodiments at least 90%, and in other embodiments at least 99% of the hydrogen atoms of the Rf group are replaced by fluorine (or in other embodiments fluorine and a complementary halogen atom). In one or more embodiments, Rf is perfluorinated.

[0022] In one or more embodiments, the polyether segment can include repeat or mer units deriving from tetrahydrofuran. In other words, the polyether may include a repeat unit described above and one or more repeat units deriving from tetrahydrofuran (THF). The source of THF can be from the BF3»THF used as a polymerization catalyst or it can be added deliberately. The level of incorporated THF can be from 1 to about 50 mole percent (optionally about 5 to about 30 mole percent).

[0023] In one or more embodiments, the polyether segment can include from about 1 to about 20 repeat or mer units, in other embodiments from about 3 to about 7 repeat or mer units, and in other embodiments from about 2 to about 5 repeat or mer units. In one or more embodiments, at least 75% of the repeat or mer units include the pendant alkoxyfluoroalkyl groups, in other embodiments at least 50% of the repeat or mer units include the pendant alkoxyfluoroalkyl groups, and in other embodiments at least 10% by weight of the repeat or mer units include the pendant alkoxyfluoroalkyl groups. [0024] In one or more embodiments, the ester component, which may be defined by the formula:

O

R— C-O- is a non-functional ester component where R is a hydrocarbyl group that does not include heteroatoms. In particular embodiments, R is an alkyl group including less than six carbon atoms, in other embodiments less than 4 carbon atoms, and in other embodiments 2 or less carbon atoms.

[0025] In one or more embodiments, the surfactants of this invention may be prepared by polymerizing cyclic ethers (e.g., oxetanes) that include pendant alkoxy fluoroalkyl groups in the presence of an initiator.

[0026] In general, the ring opening polymerization of cyclic ethers can take place within an inert solvent in the presence of a Lewis acid catalyst and an initiator. The initiator is typically a monoalcohol or polyol. Useful monoalcohols include, for example, trifluoroethanol, benzyl alcohol, allyl alcohol, heptafluorbutanol, pentafluoropropanol, pentafluorobutanol, and nonafluorohexanol. Useful polyols include, for example, ethylene glycol, butane- 1,4-diol, propylene glycol, isobutane-l,3-diol, pentane-l,5-diol, pentaerythritol, trimethylolpropane, and the like. [0027] In particular embodiments, the polyol is a polymeric polyol such as, for example, polyethylene oxide, polypropylene oxide, and copolymers of ethylene oxide and propylene oxide. In particular embodiments, the polyol is a block copolymer including a polypropylene oxide block and a polyethylene oxide block. A particular example includes b-poly (oxetane) -b-poly (ethylene oxide) -b-poly (oxetane), which is commercially available under the tradename PF-15 IN.

[0028] Methods for polymerizing cyclic ethers including pendent alkoxyfluoroalkyl groups are known as described in U.S. Patent Nos. 6,423,418, 6,383,651, 6,579,966, 6,465,565, 6,565,566, which are incorporated herein by reference. [0029] In one or more embodiment, the cyclic ether that is polymerized or oligomerized includes cyclic oxetane. One or more of the cyclic oxetane may include one or more pendant alkoxyfluoroalkyl groups. In one or more embodiments, the cyclic oxetane monomer may be defined by at least one of the formulae

or

wherein each n is, independently, 0 to about 6 wherein R is hydrogen or monovalent organic group, and wherein each Rf is, independently, a monovalent organic group with a minimum of 50% of the hydrogen atoms of said Rf group being replaced by F, and optionally up to all of the remaining H atoms being replaced by I, Cl, or B. In certain embodiments, n is an integer from 1 to 3, R is hydrogen or an alkyl group having from 1 to 6 carbon atoms, and Rf is an alkyl group including 1 to 20 carbon atoms. In these or other embodiments, Rf includes from 1 to 6, and in other embodiments from 2 to 5 carbon atoms. In these or other embodiments, at least 90% of the hydrogen atoms of Rf are replaced by fluorine. In certain embodiments, Rf is perfluorinated. In certain embodiments, these monomers are copolymerized with comonomer including THF. [0030] Depending on the functionality of the initiator employed, the polyether formed from the ring opening reaction may include one or more terminal hydroxyl groups. For example, where a monoalcohol is employed as an initiator, the polyether will include one hydroxyl end group. Alternatively, where a diol is employed as an initiator, the polyether will include two terminal hydroxyl groups (i.e., one at each end of a linear polyether chain).

[0031] In one or more embodiments, the polyether ester is formed by reacting a polyether including a pendant alkoxy fluoroalkyl group with an acid anhydride, which may be referred to simply as an anhydride. In general, where an acyclic anhydride is employed, one mole of the acyclic anhydride can be reacted with two equivalents of hydroxyl group on the polyether. And, in general, where a cyclic anhydride is employed, one mole of the cyclic anhydride may be reacted with one equivalent of hydroxyl group on the polyether.

[0032] In one or more embodiments, the anhydride is an acyclic anhydride. In one or more embodiments, acyclic anhydrides may be defined by the formula:

where R¹⁰ and R¹¹ are each independently a monovalent organic group. In particular embodiments, R¹⁰ and R¹¹ each include less than 20 carbon atoms, in other embodiments less than 10 carbon atoms, and in other embodiments less than 6 carbon atoms. [0033] Specific examples of acyclic anhydrides include formic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, caprylic anhydride, nonanoic anhydride, decanoic anhydride, lauric anhydride, palmitic anhydride, and stearic anhydride. [0034] In one or more embodiments, the anhydride is a cyclic anhydride. In one or more embodiments, cyclic anhydrides may be defined by the formula:

where R¹² is a divalent organic group.

[0035] Specific examples of cyclic anhydrides include maleic anhydride, succinic anhydride, phthalic anhydride, naphthalic anhydride, and dimethylglutaric anhydride.

[0036] In one or more embodiments, the reaction between the polyether and the acid anhydride may take place within an inert solvent. In particular embodiments, the solvent serves to solubilize the polyether and the acid anhydride. Exemplary solvents include polar organic solvents. Specific examples include those polar organic solvents in which the polyether is synthesized as disclosed above. In one or more embodiments, the concentration of the polyether within the solvent may be as low as 1% and as high as

80%.

[0037] In these or other embodiments, the reaction may take place in the presence of a Bronsted acid catalyst, which includes substances that can give up a proton. In one or more embodiments, the acid catalyst is soluble within the inert solvent in which the polyether and acid anhydride are reacted. Exemplary acid catalysts include p-toluene sulfonic acid monohydrate, and sulfuric acid.

[0038] In one or more embodiments, the reaction conditions may include heating the reaction mixture at or above the boiling point of the inert solvent. [0039] After a desired conversion of the polyether and acid anhydride to the polyether ester, the reaction can be quenched by the addition of a Bronsted base, which is believed to quench the acidic byproducts formed during the formation of the polyether ester. As is known in the art, these neutralized byproducts can then be separated from the desired polyether ester product using dual phase lipophillic/hydrophilic washing techniques.

[0040] In one or more embodiments, the compounds or surfactants of this invention are useful as fluorosurfactants. In one or more embodiments, these fluorosurfactants are useful as at least one of a wetting, flow, and leveling agent in aqueous systems. These fluorosurfactants may also be used to emulsify various polymers. Still further, these fluorosurfactants can be employed to form coatings that can demonstrate technologically useful adsorption to substrates, particularly those bearing a negative charge (e.g., glass). The polyether compounds of the present invention can also be used as wetting, leveling and flow agents in solvent-borne (i.e., non-polar) coating systems. [0041] While the amount of polyether compound of this invention that is used in various aqueous compositions may vary, it may be useful to employ from about 50 ppm to about 10 wt%, optionally from about 100 ppm to about 5 wt%, and optionally from about 500 ppm to about 1 wt% of the surfactant of this invention based upon the total weight of aqueous solution. In one or more embodiments, the coating compositions of this invention may include at least 50 ppm, in other embodiments at least 150 ppm, in other embodiments at least 250 ppm, in other embodiments at least 350 ppm, in other embodiments at least 450 ppm, in other embodiments at least 550 ppm, and in other embodiments at least 7500 ppm of the non-reactive fluorinated compound. In these or other embodiments, the compositions of this invention include less than 3000 ppm, in other embodiments less than 2000 ppm, in other embodiments less than 1500 ppm, in other embodiments less than 1200 ppm, in other embodiments less than 1000 ppm, in other embodiments less than 900 ppm, and in other embodiments at least 800 ppm of the non-reactive fluorinated compound. In one or more embodiments, use of the non- reactive fluorinated compound according to this invention allows for the use of a fraction of the non-reactive fluorinated compound as compared to similar compositions that employ reactive fluorinated compounds (i.e. those that chemically incorporate into the cured coating composition) even though the fluorinated compound may otherwise be similar except for its ability to react into the coating. In one or more embodiments, practice of present invention achieves at least equal results in wetting, flow and/or leveling as similar compositions with similar fluorinated, but reactive, compounds at less than 75%, in other embodiments less than 65%, in other embodiments less than 55%, in other embodiments less than 45%, and in other embodiments less than 35% of the concentration.

[0042] The polyether compounds can have a beneficial impact on several types of aqueous compositions. These aqueous compositions include, but are not limited to, floor polish, aqueous paints, spin-on coatings (e.g., semiconductor cleaning solutions, dielectric compositions, and photo resist compositions), cleaning formulations, leather coatings, and wood coatings.

[0043] The polyether esters of one or more embodiments of the present invention show one or more technological advantages. For example, the presence of the acetate, which effectively end-caps the polyether segment, provides a polyether with reduced reactivity, particularly reactivity with compounds that react with a hydroxyl group. It has unexpectedly been discovered that polyether esters according to the present invention show more effective surface tension reduction below the critical micelle concentration and/or aggregation limit as compared to similar polyethers without an acetate end group (i.e., an ester), even though the polymers may show similar surface tension reduction a the aggregation limit.

[0044] In one or more embodiments, the coating compositions of this invention are useful for forming curable films that have advantageous properties. These films can be prepared by employing conventional techniques such rolling, spraying, knife-coating, and the like. As is generally known in the art, these films may have an uncured thickness of at least 0.01 mm, or in other embodiments at least 0.05, or in other embodiments at least 0.1 mm. In these or other embodiments, the uncured coating compositions can have a film thickness of less than 3 mm, in other embodiments less than 1.5 mm, in other embodiments less than 1, or in other embodiments less than 0.5 mm.

[0045] In order to demonstrate the practice of the present invention, the following examples have been prepared and tested. The examples should not, however, be viewed as limiting the scope of the invention. The claims will serve to define the invention.

EXAMPLES Example 1

[0046] A 500 ml 3-necked round-bottomed flask was equipped with a condenser, Temperature probe, pressure equalizing addition funnel, and heating mantle. The flask was charged with polyoxetane (Le., polyether) obtained under the tradename PolyFox™ PF-151N (OMNOVA Solutions Inc.) (100 grams, 0.07 moles OH), p-toluene sulfonic acid monohydrate (0.5 grams, 0.00263 moles), and 100 grams methylene chloride. Acetic anhydride (9.03 grams, 0.09 moles) was added dropwise over 15 minutes. The reaction was heated to 39 C (reflux) for 1 hour. Conversion was followed with ¹H-NMR, and heating was continued until the reaction was complete. The reaction mixture was quenched with aqueous ammonia (10.75 grams, 0.18 moles), and washed with 50 grams of water. The organic layer was separated, and the methylene chloride was removed to afford acetate capped product in quantitative yield (95 grams). Example 2

[0047] A 500 ml 3-necked round-bottomed flask was equipped with a condenser, Temperature probe, pressure equalizing addition funnel, and heating mantle. The flask was charged with polyoxetane (i.e., polyether) obtained under the tradename PolyFox™ PF-656 (OMNOVA Solutions Inc.) PolyFox PF-656 (100 grams, 0.13 moles OH), p-toluene sulfonic acid monohydrate (2.44 grams, 0.013 moles), and 100 grams methylene chloride. Acetic anhydride (15.51 grams, 0.15 moles) was added dropwise over 15 minutes. The reaction was heated to 39 C (reflux) for 1 hour. Conversion was followed with ¹H-NMR, and heating was continued until the reaction was complete. The reaction mixture was quenched with aqueous ammonia (18.46 grams, 0.30 moles), and washed with 100 grams of water. The organic layer was separated, and the methylene chloride was removed to afford acetate capped product in quantitative yield (103 grams). [0048] Various modifications and alterations that do not depart from the scope and spirit of this invention will become apparent to those skilled in the art. This invention is not to be duly limited to the illustrative embodiments set forth herein.

Claims

CLAIMSWhat is claimed is:

1. A coating composition comprising: (i) a curable component; and

(ii) a fluorine-containing compound that is non-reactive with the curable component; where the fluorine-containing compound is a polyether ester defined by the formula:

O

R-C-O — α where R includes a monovalent organic group and α is a polyether including at least one pendant alkoxy fluoroalkyl group.

2. The coating composition of claim 1, where the composition includes less than 3000 ppm of the fluorinated compound.

3. The coating composition of claims 1-2, where the composition includes less than 2000 ppm of the fluorinated compound.

4. The coating composition of claims 1-3, where the composition includes less than 1000 ppm of the fluorinated compound.

5. The coating composition of claims 1-4, where R is an alkyl group including less than 6 carbon atoms.

6. The coating composition of claims 1-5, where said polyether segment includes at least one repeat unit defined by the formula Rf

where Rl is a monovalent organic group or a substituent defined by the formula — R2 — O — R3 — Rf, R2 is a divalent organic group, R^ is a divalent organic group or a bond, and Rf is a monovalent organic group with at least 25% of the hydrogen atoms being replaced by fluorine.

7. The coating composition of claims 1-6, where said polyether segment is defined by one or more of the formulae

or

£CH₂)_m-0 (CH₂)_n R_f where m is an integer from 1 to about 3, n is an integer from about O to 3, Rl is a hydrogen atom or monovalent organic group, and Rf is a linear or branched alkyl group including 1 to about 20 carbon atoms with at least 25% of the hydrogen atoms being replaced by fluorine.

8. The coating composition of claims 1-7, where said polyether segment includes from about 1 to about 20 repeat or mer units.

9. The coating composition of claims 1-8, where at least 75% of the repeat or mer units of said polyether segment include the pendant alkoxyfluoroalkyl groups.

10. The coating composition of claims 1-9, where said polyether segment includes repeat or mer units deriving from tetrahydrofuran.

11. The coating composition of claims 1-10, where Rf is perfluorinated.

12. The coating composition of claims 1-11, where the curable component includes an isocyanate.

13. The coating composition of claims 1-11, where the curable component includes a dicarboxylic acid.

14. The coating composition of claims 1-11, where the curable component includes an amino resin.

15. A coating composition comprising:

(i) a curable component; and

(ii) a fluorine-containing compound prepared by a method comprising:

(i) providing an initiator compound including at least one hydroxyl group; (ii) initiating the polymerization of cyclic ether monomers with the initiator compound, where the monomers include one or more monomer having a pendant alkoxyfluoroalkyl group to provide a polyether precursor compound; and (iii) reacting the polyether precursor compound with an acid anhydride.

16. The coating composition of claim 15, where said acid anhydride is defined by the formula

where R¹⁰ and R¹¹ are each independently a monovalent organic group.

17. The coating composition of claim 15-16, wherein said acid anydride is selected from the group consisting of formic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, hexanoic anhydride, heptanoic anhydride, caprylic anhydride, nonanoic anhydride, decanoic anhydride, lauric anhydride, palmitic anhydride, and stearic anhydride.

18. The coating composition of claim 15-17, where said anhydride is defined by the formula

where R¹² is a divalent organic group.

19. The coating composition of claim 15-18, where said anhydride is selected from the group consisting of maleic anhydride, succinic anhydride, phthalic anhydride, naphthalic anhydride, and dimethylglutaric anhydride.

20. A coating composition comprising:

(i) a curable component; and

(ii) a fluorine-containing compound prepared by method comprising:

(i) providing a polyether having a pendant alkoxyfluoroalkyl group; and (ii) reacting the polyether with an acid anhydride.

21. A curable film formed from a coating composition, the coating composition including (i) a curable component; and (ii) a fluorine-containing compound that is non- reactive with the curable component; where the fluorine-containing compound is a polyether ester defined by the formula:

O

R-C-O — α where R includes a monovalent organic group and α is a polyether including at least one pendant alkoxy fluoroalkyl group.

22. A cured coating including a polyether ester defined by the formula:

O

R-C-O — α where R includes a monovalent organic group and α is a polyether including at least one pendant alkoxy fluoroalkyl group, where the cured coating includes a cross-linked component and where the polyether ester is not chemically bound to the cross-linked component.

23. The coating of claim 22, where the cross-linked component is a polyurethane or a polyester.