WO2015142559A1

WO2015142559A1 - Fluorinated compound, fluorinated polymer formed from same, curable composition comprising the fluorinated polymer, and cured product

Info

Publication number: WO2015142559A1
Application number: PCT/US2015/019559
Authority: WO
Inventors: Dorab Edul Bhagwagar; Jing Jiang; Don Lee Kleyer; William James Schulz
Original assignee: Dow Corning Corporation
Priority date: 2014-03-17
Filing date: 2015-03-10
Publication date: 2015-09-24
Also published as: TW201609873A

Abstract

A fluorinated compound has the general formula (1 ): R_f-CONR-(CH₂)_a-SiR1 X-(OSiR¹ X)_b-(CH₂)_c-Y (1 ); wherein R_f is a fluoro-substituted group; R is H or a substituted or unsubstituted hydrocarbyl group; each R¹ is an independently selected substituted or unsubstituted hydrocarbyl group; each X is independently R¹ or an amine-containing group; Y is a terminal group selected from R and X; subscripts a and c are each are each independently selected from 0 and an integer from 1 to 10; and subscript b is an integer from 2 to 20; with the proviso that the fluorinated compound includes at least one amine- containing group. A fluorinated polymer comprises the reaction product of a Michael addition reaction of the fluorinated compound and a polyfunctional acrylate. A curable composition comprising the fluorinated polymer, a cured product formed from the curable composition, and a method of forming the cured product are also disclosed.

Description

FLUORINATED COMPOUND, FLUORINATED POLYMER FORMED FROM SAME, CURABLE COMPOSITION COMPRISING THE FLUORINATED

POLYMER, AND CURED PRODUCT

FIELD OF THE INVENTION

[0001] The present invention generally relates to a fluorinated compound and, more specifically, to a fluorinated compound, a fluorinated polymer formed from the fluorinated compound, a curable composition comprising the fluorinated polymer, a cured product formed from the curable composition, and a method of forming the cured product with the curable composition.

DESCRIPTION OF THE RELATED ART

[0002] Fluorinated compounds are known in the art and are utilized in various applications and end uses. For example, fluorinated compounds are commonly utilized in curable compositions. The curable compositions are applied to substrates and cured to form layers or coatings on the substrates.

[0003] Layers formed from curable compositions comprising fluorinated compounds may have diverse and desirable physical properties contingent on the components of the curable compositions. Such layers may be utilized to modify or improve physical properties of or otherwise protect the substrate. For example, certain layers are commonly utilized for smudge and stain resistance or to provide surfaces that are easy to clean. Other layers are utilized for providing protection to the underlying substrate, such as water repellency and/or resistance to scratching.

[0004] It is desirable for the curable compositions to have excellent physical properties, such as storage stability. Such physical properties associated with the curable compositions must be balanced with the desired properties of the resulting layers formed from the curable compositions. For example, it is desirable for the layers to have high adhesion to the substrate while providing scratch resistance and easy to clean surfaces.

SUMMARY OF THE INVENTION

[0005] The invention provides a fluorinated compound. The fluorinated compound has the general formula (1 ):

Rf-CONR-(CH2)_a-SiR¹ X-(OSiR¹ X)_b-(CH₂)c-Y (1 );

wherein Rf is a fluoro-substituted group; R is H or a substituted or unsubstituted hydrocarbyl group; each R¹ is an independently selected substituted or unsubstituted hydrocarbyl group; each X is independently R¹ or an amine-containing group; Y is a terminal group selected from R and X; subscripts a and c are each are each independently selected from 0 and an integer from 1 to 10; and subscript b is an integer from 2 to 20; with the proviso that the fluorinated compound includes at least one amine-containing group designated by X or Y.

[0006] The invention also provides a fluorinated polymer. The fluorinated polymer comprises the reaction product of a Michael addition reaction of the fluorinated compound and a polyfunctional acrylate.

[0007] Further, the invention provides a curable composition comprising the fluorinated polymer and a polyfunctional acrylate. The invention additionally provides a cured product formed from the curable composition.

[0008] Finally, the invention provides a method of forming the cured product. The method comprises applying the curable composition on a substrate. The method further comprises curing the curable composition on the substrate so as to form the cured product on the substrate.

DETAILED DESCRIPTION OF THE INVENTION

[0009] The invention provides a fluorinated compound. The fluorinated compound is particularly suitable for forming a fluorinated polymer, e.g. for a curable composition. In these embodiments, the fluorinated compound may alternatively be referred to as a fluorinated intermediate. The fluorinated compound, fluorinated polymer, curable composition, cured product formed from the curable composition, and method of forming the cured product are described below.

[0010] The fluorinated compound has the general formula (1 ):

Rf-CONR-(CH2)a-SiR¹ X-(OSiR¹ X)_b-(CH₂)c-Y (1 );

[0011] Rf of general formula (1 ) is a group that is fluoro-substituted. By fluoro-substituted, it is meant that at least one portion, segment, or moiety of Rf is fluoro-substituted. Rf may be partially fluorinated or perfluorinated. By partially fluorinated, it means that Rf may be monofluorinated or polyfluorinated, but not perfluorinated. For example, partially fluorinated encompasses mono-fluorination, where there is but one fluorine substitution in Rf, and polyfluorination, where there are two or more fluorine substitutions in Rf. Rf is monovalent.

[0012] For example, Rf may be an organic group or segment, a silicone group or segment, or combinations thereof. Organic groups, as used herein, are distinguished from silicone groups, with silicone groups having a backbone comprising siloxane bonds (Si-O-Si) and organic groups having a backbone that is carbon-based and lacking siloxane bonds. Rf may comprise both siloxane bonds and carbon bonds in the backbone.

[0013] When Rf is a silicone group, the fluoro-substitution is generally present in one or more hydrocarbyl substituents bonded to silicon. Said differently, the fluorine atom(s) are generally not bonded directly to silicon atoms. For example, the silicon atoms of the silicone group generally each have two substituents in addition to the siloxane bonds, and these substituents may independently be fluoro-substituted. As one specific example, when Rf is a silicone group,

Rf may comprise the group Si(CF3)20, where CF3 groups are representative of the fluoro- substitution. Because Rf need not be perfluorinated, this one group of Rf may alternatively be, for example, Si(CFH2)(CH3)0, where there is but one fluorine substitution. This specific group, if present in Rf, is generally endblocked, e.g. trihydrocarbyl endblocked, as Rf is monovalent.

[0014] Alternatively, as set forth above, Rf may be a fluoro-substituted organic group or segment. In these embodiments, Rf may be, for example, a fluoro-substituted alkyl group or a fluoro-substituted alkoxy group. The alkoxy group may independently repeat. When Rf is a fluoro-substituted alkyl group, Rf typically comprises repeating CF2 groups with a terminal CF3 group (if perfluorinated). When Rf is a fluoro-substituted alkoxy group, Rf includes one or more oxygen atoms and may comprise OCH2 groups and CF2 groups with a terminal CF3 group. .

[0015] In certain embodiments, Rf: (i) is partially fluorinated; (ii) comprises a perfluoropolyether segment; or (iii) both (i) and (ii). When Rf is both (i) and (ii), Rf includes a substituent, moiety, or group that is not perfluorinated such that although Rf comprises a perfluorinated segment, the Rf as an overall group is segment is not perfluorinated, but rather partially fluorinated.

[0016] When Rf comprises the perfluoropolyether segment, specific examples of moieties that may be present in R_f include -(CF₂)-, -(CF(CF₃)CF₂0)-, -(CF₂CF(CF₃)0)-, -(CF(CF₃)0)-, - (CF(CF₃)-CF₂)-, -(CF₂-CF(CF₃))-, and -(CF(CF₃))-. Such moieties may be present in any order within the perfluoropolyether segment of Rf and may be in randomized or block form. Each moiety may independently be present two or more times in the perfluoropolyether segment of Rf. Generally, the perfluoropolyether segment of Rf is free from oxygen-oxygen bonds, with oxygen generally being present as a heteroatom between adjacent carbon atoms so as to form an ether linkage. The perfluoropolyether segment may terminate with a CF3 group.

[0017] In one specific embodiment when of Rf comprises the perfluoropolyether segment, the perfluoropolyether segment comprises moieties having the general formula (5):

-(C₃F₆0)_x-(C2F₄0)_y-(CF2)_z- (5);

wherein subscripts x, y, and z are each independently selected from 0 and an integer from 1 to 40, with the proviso that all three of x, y, and z are not simultaneously 0. If x and y are both 0, then z is an integer from 1 to 40 and at least one other perfluoroether moiety is present in the perfluoropolyether segment. The subscripts y and z may be 0 and x is selected from integers from 1 to 40, alternatively the subscripts x and y is 0 and z is selected from integers from 1 to 40; alternatively the subscripts x and z is 0 and y is selected from integers from 1 to 40. The subscript z may be 0 and x and y are each independently selected from integers from 1 to 40, alternatively the subscript y is 0 and x and z are each independently selected from integers from 1 to 40; alternatively the subscript x is 0 and y and z are each independently selected from integers from 1 to 40.. Typically, x, y, and z are each independently selected from integers from 1 to 40. The moieties represented by subscripts x and y may be independently branched or linear. For example, (C3FgO) may independently be represented by CF2CF2CF2O,

CF(CF₃)CF₂0 or CF₂CF(CF₃)0.

[0018] Specific examples of Rf include any of the polyfluoropolyether segments suitable for the polyfluoropolyether silanes disclosed in co-pending U.S. Appln. Publ. No. US 2014/02721 1 1 A1 , which is incorporated by reference herein in its entirety.

[0019] R is H or a substituted or unsubstituted hydrocarbyl group. When R is the substituted or unsubstituted hydrocarbyl group, R typically is a C-1 -C22 hydrocarbyl group, which may be linear, branched, and/or cyclic. Cyclic hydrocarbyl groups encompass aryl groups as well as saturated or non-conjugated cyclic groups. By "substituted," it is meant that one or more hydrogen atoms may be replaced with atoms other than hydrogen (e.g. a halogen atom, such as chlorine, fluorine, bromine, or iodine.); alternatively oxygen, sulfur, or nitrogen. Typically, R is a C1 -C4 alkyl group.

[0020] Each X is independently R1 or an amine-containing group. When X is the amine- containing group, the nitrogen of the amine-containing group may be primary, secondary, or tertiary. When more than one X of the fluorinated compound is the amine-containing group, each X may be independently selected from these amine-containing groups. In various embodiments, the amine-containing group is primary such that the nitrogen atom of the amine- containing group is bonded to two hydrogen atoms (-NH2), i.e., the amine-containing group may be an amino group. The amine-containing group may be bonded to a carbon atom of the backbone of the fluorinated compound or a silicon atom of the backbone of the fluorinated compound. The nitrogen atom of the amine-containing group may be bonded directly to carbon and/or silicon in the backbone of the fluorinated compound or the nitrogen atom may be bonded to the carbon and/or silicon in the backbone of the fluorinated compound via a bivalent linking group, such as a hydrocarbylene, heterohydrocarbylene, or organoheterylene linking group. For example, in these embodiments the amine-containing group may be selected from a 2- aminoethyl group, a 3-aminopropyl group, a 3-(2-aminoethyI) aminopropyl group, and/or a 6- aminohexyl group.

[0021] In certain embodiments of the fluorinated compound, R is H such that the fluorinated compound has the general formula (2):

Rf-CONH-(CH₂)_a- SiR¹ X-(OSiR¹ X)_b-(CH₂)_c-Y (2);

wherein Rf, R¹ , X, Y, and subscripts a, b, and c are defined above.

[0022] In these or other embodiments, X is R¹ and Y is an amine-containing group such that the fluorinated compound has the general formula (3):

Rf-CONH-(CH₂)_a- SiR¹ ₂-(OSiR¹2)b-(CH₂)c-NHR (3);

wherein Rf, R, R¹ , and subscripts a, b, and c are defined above.

[0023] In these or other embodiments, subscripts a and c are each 0 such that the fluorinated compound has the general formula (4):

Rf-CONH- SiR¹ ₂-(OSiR¹ ₂)b-NHR (4);

wherein Rf, R, R¹ , and subscript b are defined above.

[0024] The fluorinated compound may be prepared via various synthetic pathways. For example, the fluorinated compound may be prepared by reacting a carboxylic ester compound and a silicone diamine compound. The carboxylic ester compound typically has the general formula (6):

Rf-COOR¹ (6); wherein Rf and R1 are defined above. The silicone diamine compound typically has the general formula (7):

RHN-(CH₂)_a-SiR¹ X-(OSiR¹ X)_b-(CH₂)c-Y (7);

wherein R¹ , R, X, and subscript b are defined above.

[0025] To increase reactivity and decrease steric hindrance of the silicone diamine compound, each R is typically H. R¹ of the carboxylic ester compound is typically methyl. In these embodiments, the carboxylic ester compound may be referred to as a methyl ester compound. As with the fluorinated compound, subscripts a and c of the silicone diamine compound are typically each 0.

[0026] The carboxylic ester compound and the silicone diamine compound are typically reacted in a molar ratio of 10:1 to 1 :10; alternatively from 5:1 to 1 :5; alternatively from 2:1 to 1 :2; of the carboxylic ester compound to the silicone diamine compound. The carboxylic ester compound and the silicone diamine compound generally react at a 1 :1 molar ratio. However, either the carboxylic ester compound or the silicone diamine compound may be utilized in a molar excess relative to the other compound.

[0027] The carboxylic ester compound is generally electrophilic and the silicone diamine compound is generally nucleophilic, and the reaction between the carboxylic ester compound and the silicone diamine compound may be referred to as amidation of the carboxylic ester compound. The carboxylic ester compound and the silicone diamine compound may be reacted to form the fluorinated compound via various techniques. For example, the carboxylic ester compound and the silicone diamine compound may be disposed in a vessel, optionally in the presence of a solvent, vehicle, and/or catalyst. Solvent can be any solvent different from the carboxylic ester compound and the silicone diamine compound that is capable of solubilizing the carboxylic ester compound and/or the silicone diamine compound. The vehicle may differ from the solvent in that the vehicle only partially solubilizes, alternatively does not solubilize, the fluorinated compound and/or the polyfunctional acrylate. Typically, the vehicle is utilized and one specific example thereof is 1 ,3-bistrifluoromethyl benzene.

[0028] The vessel is typically heated to an elevated temperature, e.g. from 50 to 150, alternatively from 75 to 125, alternatively from 90 to 1 10, degrees Celsius CO). The vessel may be heated at the elevated temperature for a period of time to effect the reaction between the carboxylic ester compound and the silicone diamine compound, e.g. from 15 to 240, alternatively from 15 to 120, alternatively from 30 to 90, minutes. [0029] The carboxylic ester compound and the silicone diamine compound react to form the fluorinated compound in accordance with the following reaction:

Rf-COOR¹ + RHN-(CH₂)_a-SiR¹ X-(OSiR¹ X)_b-(CH₂)c-Y -» Rf-CONR-(CH₂)_a-SiR¹ X- (OSiRl X)_b-(CH₂)c-Y.

[0030] One of skill in the art readily understands how to modify the silicone diamine compound based on the desired structure of the resulting fluorinated compound. For example, X may be different substituents, as described above, and one of skill in the art understands how to modify or select the proper silicone diamine compound so as to form the desired fluorinated compound.

[0031] Progress of the reaction to form the fluorinated compound may be monitored via various techniques, such as spectroscopy, e.g. infrared (IR) spectroscopy.

[0032] The fluorinated compound may be utilized in various compositions, end uses, and/or applications. Because the fluorinated compound includes at least one amine-containing group, the fluorinated compound may be referred to as reactive, as amine-containing groups are reactive with certain functional groups. The fluorinated compound may be utilized as a discrete component, disposed in a solvent or vehicle to form a composition, combined with one or more other components to form a composition, reacted with another compound, etc. Alternatively still, the fluorinated compound may be utilized for surface treatment, either discretely or in a composition, for various substrates, such as ceramic, glass, or stone. Further, the fluorinated compound may be utilized in coating compositions, such as paints, or to modify other polymers.

[0033] The invention additionally provides a fluorinated polymer. The fluorinated polymer is formed from the fluorinated compound. The fluorinated polymer comprises the reaction product of a Michael addition reaction of the fluorinated compound and a polyfunctional acrylate. Michael addition reactions are known in the art and involve nucleophilic addition. More specifically, the amine-containing group of the fluorinated compound reacts with an acrylate functional group of the polyfunctional acrylate via the Michael addition reaction to form the fluorinated polymer.

[0034] By "polyfunctional," with reference to the polyfunctional acrylate, means that the polyfunctional acrylate is at least bifunctional, i.e., has two or more acrylate functional groups. In certain embodiments, the polyfunctional acrylate has at least 3, alternatively at least 4, alternatively at least 5, alternatively at least 6, alternatively at least 7, alternatively at least 8, alternatively at least 9, alternatively at least 10, acrylate functional groups. Higher functionalities may also be suitable, e.g. an icosafunctional acrylate. The polyfunctional acrylate may be monomeric, oligomeric, or polymeric in nature, and may comprise combinations thereof. For example, the polyfunctional acrylate may comprise a combination of a monomeric polyfunctional acrylate and an oligomeric polyfunctional acrylate. The polyfunctional acrylate may be linear, branched, or a combination of linear and branched polyfunctional acrylates.

[0035] The polyfunctional acrylate may be organic or silicone-based. When the polyfunctional acrylate is organic, the polyfunctional acrylate comprises a carbon-based backbone or chain, optionally with heteroatoms, such as O, therein. Alternatively, when the polyfunctional acrylate is silicone-based, the polyfunctional acrylate comprises a siloxane-based backbone or chain comprising siloxane (Si-O-Si) bonds. The polyfunctional acrylate may comprise both a carbon- based chain and a siloxane-based chain, such as if the polyfunctional acrylate is formed via hydrosilylation, in which case the polyfunctional acrylate is still referred to as being silicone- based due to the presence of siloxane bonds therein. In certain embodiments, when the polyfunctional acrylate is organic, the polyfunctional acrylate is free from any siloxane bonds, alternatively free from any silicon atoms. Typically, the polyfunctional acrylate is organic.

[0036] Specific examples of polyfunctional acrylates suitable for reacting with the fluorinated compound to form the fluorinated polymer include: difunctional acrylate monomers, such as 1 ,6- hexanediol diacrylate, 1 ,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, 1 ,4-butanediol dimethacrylate, poly(butanediol) diacrylate, tetraethylene glycol dimethacrylate, 1 ,3-butylene glycol diacrylate, triethylene glycol diacrylate, triisopropylene glycol diacrylate, polyethylene glycol diacrylate and bisphenol A dimethacrylate; trifunctional acrylate monomers, such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol monohydroxytriacrylate and trimethylolpropane triethoxytriacrylate; tetrafunctional acrylate monomers, such as pentaerythritol tetraacrylate and ditrimethylolpropane tetraacrylate; penta- or higher polyfunctional monomers, such as dipentaerythritol hexaacrylate and dipentaerythritol (monohydroxy)pentaacrylate; bisphenol A epoxy diacrylate; hexafunctional aromatic urethane acrylate, aliphatic urethane diacrylate, and an acrylate oligomer of tetrafunctional polyester acrylate.

[0037] The polyfunctional acrylate may comprise a single polyfunctional acrylate or any combination of two or more polyfunctional acrylates. In certain embodiments, the polyfunctional acrylate comprises a penta- or higher polyfunctional acrylate, such as any polyfunctional acrylate from a pentafunctional acrylate to an icosafunctional acrylate, which may improve curing of the curable composition. For example, in certain embodiments, the polyfunctional acrylate comprises the penta- or higher polyfunctional acrylate in an amount of at least 30, alternatively at least 50, alternatively at least 75, alternatively at least 80, percent by weight based on the total weight of the polyfunctional acrylate. Typically, the polyfunctional acrylate is free from any fluorine atoms, such as in fluoro-substituted groups.

[0038] When the fluorinated compound is utilized to form the fluorinated polymer, the fluorinated polymer may optionally be formed in the same vessel as the fluorinated compound. For example, upon reacting the carboxylic ester compound and the silicone diamine compound to form the fluorinated compound, the polyfunctional acrylate may be disposed in the vessel to react with the fluorinated compound and form the fluorinated polymer. The polyfunctional acrylate may be disposed in the vessel prior to, during, or after the reaction between the carboxylic ester compound and the silicone diamine compound. Alternatively, the fluorinated compound may be isolated or purified if any residual amounts of the carboxylic ester compound and/or the silicone diamine compound are present in the vessel. Alternatively still, the fluorinated compound may be prepared and subsequently stored or transported to a different vessel or geographic location prior to reacting with the polyfunctional acrylate to form the fluorinated polymer.

[0039] Generally one acrylate functional group of one molecule of the polyfunctional acrylate reacts with one amine-containing group of one molecule of the fluorinated compound. In certain embodiments, there is but one amine-containing group in one molecule of the fluorinated compound. Typically, the amine-containing group is terminal such that the resulting fluorinated polymer is linear. However, the amine-containing group may be pendant in the fluorinated compound such that the fluorinated polymer is branched. Further, the fluorinated compound may have two or more amine-containing groups. In these embodiments, each of the amine- containing groups of the fluorinated compound may react with an acrylate functional group of the polyfunctional acrylate (and optionally each of the amine-containing groups of the fluorinated compound may react with an acrylate functional group of different polyfunctional acrylate molecules).

[0040] The molar ratio of the fluorinated compound and the polyfunctional acrylate may vary. For example, when the fluorine compound includes but one amine-containing group, one mole of the fluorine containing group may react with one mole of the polyfunctional acrylate. However, because the polyfunctional acrylate includes two or more acrylate functional groups, two moles of the fluorine compound may react with one mole of the polyfunctional acrylate. Further, when the fluorinated compound includes two or more amine-containing groups, one mole of the fluorinated compound may react with more than one mole of the polyfunctional acrylate. The fluorine compound and the polyfunctional acrylate are typically reacted in a molar ratio of 10:1 to 1 :10; alternatively from 5:1 to 1 :5; alternatively from 2:1 to 1 :2; of the fluorine compound to the polyfunctional acrylate.

[0041] The Michael addition reaction between the fluorinated compound and the polyfunctional acrylate may optionally be carried out in the presence of a solvent, vehicle and/or catalyst. Typically, the reaction is carried out in the absence of a solvent or vehicle, i.e., neat. Solvent can be any solvent different from the fluorinated compound and the polyfunctional acrylate that is capable of solubilizing the fluorinated compound and/or the polyfunctional acrylate. The vehicle may differ from the solvent in that the vehicle only partially solubilizes, alternatively does not solubilize, the fluorinated compound and/or the polyfunctional acrylate.

[0042] Generally, no catalyst is required to initiate the Michael addition reaction between the fluorinated compound and the polyfunctional acrylate. If desired, however, catalysts may be utilized to initiate and/or accelerate the Michael addition reaction between the fluorinated compound and the polyfunctional acrylate. Suitable catalysts include bases of conjugated acids. Typically, the conjugated acids and their corresponding bases are organic. Specific examples of such bases include 1 ,4-dihydropyridines, methyl diphenylphosphane, methyl di-p- tolylphosphane, 2-allyl-N-alkyl imidazolines, tetra-t-butylammonium hydroxide, DBU (1 ,8- diazabicyclo[5.4.0]undec-7-ene) and DBN (1 ,5-diazabicyclo[4.3.0]non-5-ene), potassium methoxide, sodium methoxide, sodium hydroxide, and combinations thereof. If utilized, the catalyst is typically utilized in a concentration of from greater than 0 to 2.0, alternatively from 0.05 to 1 .0, alternatively from 0.1 to 1 .0, percent by weight based on the total weight of the fluorinated compound and the polyfunctional acrylate.

[0043] For the Michael addition reaction between the fluorinated compound and the polyfunctional acrylate, the vessel is typically heated to an elevated temperature, e.g. from 25 to 100, alternatively from 25 to 75, alternatively from 40 to 60, °C. The vessel may be heated at the elevated temperature for a period of time to effect the Michael addition reaction between the fluorinated compound and the polyfunctional acrylate, e.g. from 15 to 240, alternatively from 15 to 120, alternatively from 30 to 90, minutes.

[0044] One specific example of the Michael addition reaction mechanism between the fluorinated compound and the polyfunctional acrylate is below for illustrative purposes only:

In the Michael addition reaction mechanism above, the PFPE segment corresponds to the Rf group described above. Further, the definition of R above is limited to this schematic only for purposes of clarity.

[0045] Progress of the Michael addition reaction to form the fluorinated polymer may be monitored via various techniques, such as spectroscopy, e.g. infrared (IR) spectroscopy. The fluorinated polymer is distinguished from the fluorinated compound by virtue of its acrylate functionality and increased molecular weight. Further, the fluorinated polymer typically does not have any residual amine-containing groups. The fluorinated polymer generally includes at least one acrylate functional group such that the fluorinated polymer itself may be crosslinked or undergo further reaction with a compound or functional group reactive with acrylate functional groups.

[0046] The fluorinated polymer may be utilized in various compositions, end uses, and/or applications. The fluorinated polymer may be utilized as a discrete component, disposed in a solvent to form a composition, combined with one or more other components to form a composition, reacted with another compound, etc. Alternatively still, the fluorinated polymer may be utilized for surface treatment, either discretely or in a composition, for various substrates, such as ceramic, glass, or stone. Further, the fluorinated polymer may be utilized in coating compositions, such as paints, or to modify other polymers.

[0047] The invention additionally provides a curable composition. The curable composition comprises the fluorinated polymer and a polyfunctional acrylate.

[0048] The polyfunctional acrylate of the curable composition may be the same as or different from the polyfunctional acrylate reacted with the fluorinated compound to form the fluorinated polymer. Specific examples of suitable polyfunctional acrylates are described above. The polyfunctional acrylate may be utilized in the Michael addition reaction in a molar excess as compared to the fluorinated compound such that the curable composition may be formed in situ in the vessel upon formation of the fluorinated polymer. Typically, an additional amount of the polyfunctional acrylate is combined with the fluorinated polymer to form the curable composition. Prior to preparing the curable composition, the fluorinated polymer may be isolated or otherwise separated from any byproducts of the Michael addition reaction between the polyfunctional acrylate and the fluorinated compound or any residual amounts of the polyfunctional acrylate and/or the fluorinated compound.

[0049] In these or other embodiments, the curable composition further comprises a reinforcing filler. The reinforcing filler is utilized to provide increased hardness and scratch resistance to a cured product formed from the curable composition. The reinforcing filler generally comprises silica. The silica may be any time of silica, e.g. the silica may be fumed silica, precipitated silica, colloidal silica, etc. Typically, the reinforcing filler comprises colloidal silica.

[0050] As understood in the art, colloidal silica comprises a mixture or suspension of silica (i.e., silica particles) in a vehicle. The vehicle may alternatively be referred to as a dispersion medium. The silica particles of the colloidal silica are typically amorphous and nonporous.

[0051] The vehicle of the colloidal silica typically has a moderately low boiling point temperature for removal of the vehicle from the curable composition (and colloidal silica). For example, the vehicle typically has a boiling point temperature at atmospheric pressure (i.e., 1 atm) of from 30 to 200, alternatively from 40 to 150, °C.

[0052] Suitable vehicles for the colloidal silica include polar and non-polar vehicles. Specific examples of such vehicles include water; alcohols, such as methanol, ethanol, isopropanol, n- butanol, and 2-methylpropanol; glycerol esters, such as glyceryl triacetate (triacetin), glyceryl tripropionate (tripropionin), and glyceryl tributyrate (tributyrin); polyglycols, such as polyethylene glycols and polypropylene glycols; cellosolves, such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; dimethylacetamide; aromatics, such as toluene and xylene; acetates, such as methyl acetate; ethyl acetate; butyl acetate; ketones, such as methyl isobutyl ketone; acetic acid; and acetone. In specific embodiments, the vehicle of the colloidal silica is selected from water and an alcohol. The colloidal silica may alternatively be referred to as a colloidal silica dispersion. Two or more different vehicles may be utilized, although such vehicles are generally compatible with one another such that the colloidal silica is homogenous. The vehicle of the colloidal silica is typically present in the colloidal silica in a concentration of from, for example, 10 to 70 weight percent based on the total weight of the colloidal silica.

[0053] The silica particles of the colloidal silica typically have an average particle size less than 200 nanometers (nm), e.g. from 1 to 100, alternatively from 1 to 50 nanometer (nm).

[0054] The silica particles of the colloidal silica may be pure silicon dioxide, or may comprise a nominal amount of impurities, such as AI2O3, ZnO, and/or cations such as Na⁺, K⁺, Ca⁺⁺, Mg⁺⁺, etc.

[0055] The colloidal silica may optionally be surface treated, e.g. with a filler treating agent. The colloidal silica may be surface treated prior to incorporation into the curable composition or may be surface treated in situ.

[0056] The amount of the filler treating agent utilized to treat the colloidal silica may vary depending on various factors, such as whether the colloidal silica is treated with the filler treating agent in situ or pretreated before being incorporated into the curable composition.

[0057] The filler treating agent may comprise a silane, such as an alkoxysilane; an alkoxy- functional oligosiloxane; a cyclic polyorganosiloxane; a hydroxyl-functional oligosiloxane, such as a dimethyl siloxane; methyl phenyl siloxane; a stearate; or a fatty acid.

[0058] Alkoxysilanes suitable for the filler treating agent are exemplified by hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, phenyltrimethoxysilane, phenylethyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and a combination thereof.

[0059] Alternatively, the alkoxysilane may include an ethylenically unsaturated group. The ethylenically unsaturated group may comprise a carbon-carbon double bond, a carbon-carbon triple bond, or combinations thereof. In these embodiments, the alkoxysilane may be represented by general formula R3₍jZSi(OR⁴)3._c|. In this general formula, is a substituted or unsubstituted monovalent hydrocarbon group which contains no aliphatic unsaturated bond.

Specific examples thereof include alkyl groups, aryl groups, and fluoroalkyl groups. R⁴ is an alkyl group, typically having from 1 to 10 carbon atoms. Z is a monovalent organic group having an aliphatic unsaturated bond. Specific examples of Z include acryl group-containing organic groups, such as a methacryloxy group, an acryloxy group, a 3-(methacryloxy)propyl group and a 3-(acryloxy)propyl group; alkenyl groups, such as a vinyl group, a hexenyl group and an allyl group; a styryl group and a vinylether group. Subscript d is 0 or 1 .

[0060] Specific examples of the alkoxysilane having an ethylenically unsaturated group include 3-(methacryloxy)propyltrimethoxysilane, 3-(methacryloxy)propyltriethoxysilane, 3-(methacryloxy) propylmethyldimethoxysilane, 3-(acryloxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methylvinyldimethoxysilane and allyltriethoxysilane.

[0061] Alkoxy-functional oligosiloxanes may alternatively be used as the filler treating agent. Alkoxy-functional oligosiloxanes and methods for their preparation are known in the art. For example, suitable alkoxy-functional oligosiloxanes include those of the formula

(R50)_eSi(OSiR5₂R6)(4._e). In this formula, subscript e is 1 , 2, or 3, alternatively 3. Each R5 is independently selected from saturated and unsaturated hydrocarbyl groups having from 1 to 10 carbon atoms. Each R^ is a saturated or unsaturated hydrocarbyl group.

[0062] Alternatively, silazanes may be utilized as the filler treating agent, either discretely or in combination with, for example, alkoxysilanes.

[0063] Alternatively still, the filler treating agent may an organosilicon compound. Examples of organosilicon compounds include, but are not limited to, organochlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethyl monochlorosilane; organosiloxanes such as hydroxy-endblocked dimethylsiloxane oligomer, hexamethyldisiloxane, and tetramethyldivinyldisiloxane; organosilazanes such as hexamethyldisilazane and hexamethylcyclotrisilazane; and organoalkoxysilanes such as methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3- methacryloxypropyltrimethoxysilane. Examples of stearates include calcium stearate. Examples of fatty acids include stearic acid, oleic acid, palmitic acid, tallow, coconut oil, and combinations thereof.

[0064] A residual amount of the filler treating agent may be present in the curable composition, e.g. as a discrete component separate from the colloidal silica.

[0065] Alternatively, the silica particles of the colloidal silica need not be surface treated with the treating agent. In these embodiments, the colloidal silica may be referred to as an unmodified colloidal silica. The unmodified colloidal silica is typically in the form of an acidic or basic dispersion.

[0066] If desired, an additional filler may be present in the curable composition, e.g. a filler other than colloidal silica. Examples thereof include alumina, calcium carbonate (e.g., fumed, fused, ground, and/or precipitated), diatomaceous earth, talc, zinc oxide, chopped fiber such as chopped KEVLAR®, onyx, beryllium oxide, zinc oxide, aluminum nitride, boron nitride, silicon carbide, tungsten carbide; and combinations thereof.

[0067] The curable composition typically further comprises an alcohol-containing vehicle. The alcohol-containing vehicle may comprise, consist essentially of, or consist of an alcohol. The alcohol-containing vehicle is for dispersing the components of the curable composition. In certain embodiments, the alcohol-containing vehicle solubilizes the components of the curable composition, in which case the alcohol-containing vehicle may be referred to as an alcohol- containing solvent.

[0068] Specific examples of alcohols suitable for the alcohol-containing vehicle include methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, ethyleneglycol, diethyleneglycol, triethyleneglycol, ethyleneglycol monomethyl ether, diethyleneglycol monomethyl ether, triethyleneglycol monomethyl ether, and combinations thereof. When the alcohol-containing vehicle comprises or consists essentially of the alcohol, the alcohol-containing vehicle may further comprise an additional organic vehicle. Specific examples thereof include acetone, methylethylketone, methylisobutylketone, or similar ketones; toluene, xylene, or similar aromatic hydrocarbons; hexane, octane, heptane, or similar aliphatic hydrocarbons; chloroform, methylene chloride, trichloroethylene, carbon tetrachloride, or similar organic chlorine-containing solvents; ethyl acetate, butyl acetate, isobutyl acetate, or a similar fatty acid ester. When the alcohol-containing vehicle comprises the additional organic vehicle, the alcohol-containing vehicle typically comprises the alcohol in an amount of from 10 to 90, alternatively from 30 to 70, weight percent based on the total weight of the alcohol-containing vehicle, with the balance of the alcohol-containing vehicle being the additional organic vehicle.

[0069] The curable composition may optionally further comprise water. If utilized, water is present in the curable composition for hydrolysis of the colloidal silica. For example, as known in the art, the silica particles of the colloidal silica may include silanol groups at a surface of the silica particles. Water may be utilized as the vehicle of the colloidal silica, in which case water is not needed as a discrete component in the curable composition. Further, if the colloidal silica is already surface treated, water is similarly not typically utilized.

[0070] In various embodiments, the curable composition may additionally comprise a photopolymerization initiator. The photopolymerization initiator is most commonly utilized if the curable composition is to be cured via irradiation with electromagnetic radiation. The photopolymerization initiator may be selected from known compounds capable of generating a radical under irradiation with electromagnetic radiation, such as organic peroxides, carbonyl compounds, organic sulfur compounds and/or azo compounds. [0071] Specific examples of suitable photopolymerization initiators include acetophenone, propiophenone, benzophenone, xanthol, fluoreine, benzaldehyde, anthraquinone, triphenylamine, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3- bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4- methylbenzophenone, 4-chlorobenzophenone, 4,4-dimethoxybenzophenone, 4-chloro-4- benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylaminophenyl)ketone, benzyl methoxy ketal, 2-chlorothioxanthone, diethylacetophenone, 1 -hydroxycyclohexyl phenyl ketone, 2-methyl[4-(methylthio)phenyl]2-morpholino-1 -propanone, 2,2-dimethoxy-2- phenylacetophenone, diethoxyacetophenone, and combinations thereof.

[0072] If utilized, the photopolymerization initiator is typically present in the curable composition in an amount of from 1 to 30, alternatively 1 to 20, parts by weight, based on 100 parts by weight of the polyfunctional acrylate.

[0073] If desired, the curable composition may further comprise a silane compound. Examples thereof include tetraalkoxysilanes, such as tetramethoxysilane, tetraethoxysilane and tetraisopropoxysilane; and alkylalkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and ethyltriisopropoxysilane. The silane compound may be utilized as a discrete component or, as another example, to form a silsesquioxane in the curable composition.

[0074] Additional examples of additives that may be present in the curable composition include antioxidants; thickeners; surfactants, such as leveling agents, defoamers, sedimentation inhibitors, dispersing agents, antistatic agents and antifog additives; ultraviolet absorbers; colorants, such as various pigments and dyes; butylated hydroxytoluene (BHT); phenothiazine (PTZ); organopolysiloxanes; and combinations thereof.

[0075] The curable composition may be prepared via various methods involving the combination of the various components of the curable composition. In certain embodiments, the colloidal silica is surface treated prior to incorporation into the curable composition. The components may individually or collectively be heated before, during, or after the preparation of the curable composition.

[0076] The curable composition may be utilized in a variety of end uses and applications. Most typically, the curable composition is utilized to form a cured product. The cured product may be in the form of a fiber, a coating, a layer, a film, a composite, an article, etc. [0077] The invention additionally provides a cured product formed from the curable composition and a method of forming the cured product with the curable composition. The cured product and method of forming the cured product are described together below.

[0078] The method of forming the cured product comprises applying the curable composition on a substrate. The method further comprises curing the curable composition on the substrate so as to form the cured product on the substrate. For example, the method of forming the cured product comprises applying the curable composition on the substrate to form a wet layer thereof on the substrate. The method further comprises curing the wet layer to form the cured product.

[0079] The substrate is not limited and may be any substrate upon which it is desirable to form the cured product. For example, the substrate may comprise an electronic article, an optical article, consumer appliances and components, automotive bodies and components, polymeric articles, etc. The substrate may have any shape or configuration.

[0080] Examples of electronic articles typically include those having electronic displays, such as liquid crystal displays (LCDs), light-emitting diode (LED) displays, organic light-emitting diode (OLED) displays, plasma displays, etc. These electronic displays are often utilized in various electronic devices, such as computer monitors, televisions, smart phones, global positioning systems (GPS), music players, remote controls, hand-held video games, portable readers, automobile display panels, etc.

[0081] As introduced above, the substrate may also be a metal article, such as consumer appliances and components. Exemplary articles include a dishwasher, a stove, a microwave, a refrigerator, a freezer, etc, typically having a glossy metal appearance, such as stainless steel, brushed nickel, aluminum, etc.

[0082] Alternatively, the substrate may be a vehicle body or component such as an automotive body or component. For example, the curable composition may be applied directly on a top coat of an automobile body to form the layer, which imparts the automobile body with a glossy appearance, which is aesthetically pleasing and resists stains, such as dirt, etc., as well as smudges from fingerprints.

[0083] Examples of suitable optical articles include inorganic materials, such as glass plates, glass plates comprising an inorganic layer, ceramics, and the like. Additional examples of suitable optical articles include organic materials, such as transparent plastic materials and transparent plastic materials comprising an inorganic layer, etc. Specific examples of optical articles include antireflective films, optical filters, optical lenses, eyeglass lenses, beam splitters, prisms, mirrors, etc. [0084] Specific examples of organic materials and/or polymeric articles include polyolefins (e.g. polyethylene, polypropylene, etc.), polycycloolefins, polyesters (e.g. polyethylene terephthalate, polyethylene naphthalate, etc.), polyamides (e.g. nylon 6, nylon 66, etc.), polystyrene, polyvinyl chloride, polyimides, polyvinyl alcohol, ethylene vinyl alcohol, acrylics (e.g. polymethyl methacrylate), celluloses (e.g. triacetylcellulose, diacetylcellulose, cellophane, etc.), or copolymers of such organic polymers. It is to be appreciated that these materials may be utilized in ophthalmic elements. Non-limiting examples of ophthalmic elements include corrective and non-corrective lenses, including single vision or multi-vision lenses like bifocal, trifocal and progressive lenses, which may be either segmented or non-segmented, as well as other elements used to correct, protect, or enhance vision, including without limitation contact lenses, intra-ocular lenses, magnifying lenses and protective lenses or visors. Preferred material for ophthalmic elements comprises one or more polymers selected from polycarbonates, polyamides, polyimides, polysulfones, polyethylene terephthalate and polycarbonate copolymers, polyolefins, especially polynorbornenes, diethylene glycol-bis(allyl carbonate) polymers - known as CR39 - and copolymers, (meth)acrylic polymers and copolymers, especially (meth)acrylic polymers and copolymers derived from bisphenol A, thio(meth)acrylic polymers and copolymers, urethane and thiourethane polymers and copolymers, epoxy polymers and copolymers, and episulfide polymers and copolymers.

[0085] The substrate may comprise any of the materials described above while being different from the particular articles recited herein. For example, the substrate may comprise a metal or alloy that is not part of a consumer appliance or vehicle body.

[0086] In addition to the articles/substrates described above, the curable composition may be applied to other substrates, such as window members for automobiles or airplanes, thus providing advanced functionality.

[0087] Alternatively still, the substrate may comprise cement, stone, paper, cardboard, ceramic, etc.

[0088] Alternatively or in addition, the substrate may comprise an antireflective coating. In these embodiments, the antireflective coating may include one or more layers of material disposed on an underlying substrate. The antireflective coating generally has a lesser refractive index than the underlying substrate. The antireflective coating may be multi-layer. Multi-layer antireflective coatings include two or more layers of dielectric material on the underlying substrate, wherein at least one layer has a refractive index higher than the refractive index of the underlying substrate. Such multi-layer antireflective coatings are often referred to as antireflective film stacks. [0089] The antireflective coating may be formed from a wide variety of materials. In certain embodiments, the antireflective coating comprises a thin metal oxide film, such as a thin sputter coated metal oxide film. Alternatively, the thin metal oxide film may be formed via thermal evaporation. "Metal oxides," as used herein, include oxides of single metals (including metalloids) as well as oxides of metal alloys. One example of a metal oxide is a silicon oxide, which may be depleted of oxygen (i.e., wherein the amount of oxygen in the oxide is less than the stoichiometric amount). Additional suitable metal oxides include oxides of tin, titanium, niobium, zinc, zirconium, tantalum, yttrium, aluminum, cerium, tungsten, bismuth, indium, and mixtures thereof. Specific examples include S1O2, Sn02, T1O2, Nb205, ZnO, Zr02, a205, Y2O3, AI2O3, Ce02, WO3, B12O, Ιη2θ3, and ITO (indium tin oxide), as well as combinations and alternating layers thereof.

[0090] If desired, the underlying substrate may have a primed surface prior to deposition of the antireflective coating. For example, the primed surface may be formed by the application of a chemical primer layer, such as an acrylic layer, or from chemical etching, electronic beam irradiation, corona treatment, plasma etching, or coextrusion of adhesion promoting layers. Such primed substrates are commercially available.

[0091] The method by which the curable composition is applied on the substrate may vary. For example, in certain embodiments, the step of applying the curable composition on the substrate uses a wet coating application method. Specific examples of wet coating application methods suitable for the method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, sputtering, slot coating, and combinations thereof. The alcohol- containing vehicle, along with any other vehicles or solvents preset in the curable composition and wet layer, may be removed from the wet layer via heating or other known methods.

[0092] The curable composition may be applied on the substrate to any thickness to provide the desired level of water, oil, stain, and soil repellency. In certain embodiments, the cured product may alternatively be referred to as a layer or film, although the cured product may have any shape or form other than that associated with layers or films. In these embodiments, the cured product has a thickness of from greater than 0 to 20, alternatively from greater than 0 to 10, alternatively from greater than 0 to 5, micrometers (μηι). In certain embodiments, the cured product has a thickness of at least 15, alternatively at least 20, alternatively at least 30, Angstroms, with the upper limit in such embodiments being 20 micrometers (μηι).

[0093] The curable composition, as well as the wet layer formed therefrom, can be rapidly cured by being irradiated with active-energy rays (i.e., high-energy rays). The active-energy rays may comprise ultraviolet rays, electron beams, or other electromagnetic waves or radiation. The use of ultraviolet rays is preferable from the point of view of low cost and high stability. A source of ultraviolet radiation may comprise a high-pressure mercury lamp, medium-pressure mercury lamp, Xe-Hg lamp, or a deep UV lamp.

[0094] The step of curing the wet layer generally comprises exposing the wet layer to radiation at a dosage sufficient to cure at least a portion, alternatively the entirety, of the wet layer. The dosage of radiation for curing the wet layer is typically from 10 to 8000 milliJoules per centimeter squared (mJ/cm^). In certain embodiments, heating is used in conjunction with irradiation for curing the wet layer. For example, the wet layer may be heated before, during, and/or after irradiating the wet layer with active-energy rays. While active energy-rays generally initiate curing of the curable composition, residual amounts of the alcohol-containing vehicle or any other vehicles and/or solvents may be present in the wet layer, which may be volatilized and driven off by heating. Typical heating temperatures are in the range of from 50 to 200 °C. Curing the wet layer provides the cured product.

[0095] The cured product has excellent physical properties and is suitable for use as protective coatings on a variety of substrates. For example, the cured product has excellent (i.e., high) hardness, durability, adhesion to the substrate, and resistance to staining, smudging, and scratching. In certain embodiments, the cured product has a water contact angle of at least 90, alternatively at least 100, alternatively at least 105, alternatively at least 108, alternatively at least 1 10, degrees ( °). In these embodiments, the upper limit is typically 120°. The water contact angle of the cured product is typically within this range even after subjecting the cured product to an abrasion test, which illustrates the excellent durability of the cured product. For example, for cured products having a lesser durability, the water contact angle decreases after abrasion, which generally indicates that the cured product has at least partially deteriorated.

[0096] In these embodiments, the cured product also typically has a sliding (kinetic) coefficient of friction (μ) of from greater than 0 to less than 0.2, alternatively from greater than 0 to less than 0.15, alternatively from greater than 0 to less than 0.125, alternatively from greater than 0 to less than 0.10. Although coefficient of friction is unitless, it is often represented by μ.

[0097] For example, sliding (kinetic) coefficient of friction may be measured by disposing an object having a determined surface area and mass onto the cured product with a select material (e.g. a standard piece of legal paper) between the object and the cured product. A force is then applied perpendicular to gravitational force to slide the object across the cured product for a predetermined distance, which allows for a calculation of the sliding coefficient of friction of the cured product. [0098] In some embodiments the invention is any one of the following numbered aspects.

[0099] Aspect 1 . A fluorinated compound having the general formula (1 ): Rf-CONR-(CH2)_a-

SiR¹ X-(OSiR¹ X)|_:)-(CH2)_c-Y (1 ); wherein Rf is a fluoro-substituted group; R is H or a substituted or unsubstituted hydrocarbyl group; each R¹ is an independently selected substituted or unsubstituted hydrocarbyl group; each X is independently R¹ or an amine-containing group; Y is a terminal group selected from R and X; subscripts a and c are each are each independently selected from 0 and an integer from 1 to 10; and subscript b is an integer from 2 to 20; with the proviso that said fluorinated compound includes at least one amine-containing group designated by X or Y.

[00100] Aspect 2. The fluorinated compound of aspect 1 wherein R is H such that said fluorinated compound has the general formula (2): R_f-CONH-(CH₂)_a- SiR¹ X-(OSiR¹ X)b- (CH2)_C-Y (2); wherein Rf, R¹ , X, Y, and subscripts a, b, and c are as defined in aspect 1 .

[00101] Aspect 3. The fluorinated compound of aspect 2 wherein X is R¹ and Y is an amine- containing group such that said fluorinated compound has the general formula (3): Rf-CONH-

(CH2)_a- SiR¹2-(OSiR¹2)b-(CH2)_c-NHR (3); wherein Rf, R, R¹ , and subscripts a, b, and c are as defined in aspect 1 .

[00102] Aspect 4. The fluorinated compound of aspect 3 wherein subscripts a and c are each 0 such that said fluorinated compound has the general formula (4): Rf-CONH- SiR¹2-(OSiR¹2)b^_ NHR (4); wherein Rf, R, R¹ , and subscript b are as defined in aspect 1 .

[00103] Aspect 5. The fluorinated compound of any one preceding aspect wherein Rf: (i) is partially fluorinated; (ii) comprises a perfluoropolyether segment; or (iii) both (i) and (ii).

[00104] Aspect 6. The fluorinated compound of aspect 5 wherein Rf comprises said perfluoropolyether segment, said perfluoropolyether segment comprising moieties of general formula (5): (C3FgO)_x-(C2F40)y-(CF2)_z- (5); wherein subscripts x, y, and z are each independently selected from 0 and an integer from 1 to 40, with the proviso that x, y, and z are not simultaneously 0.

[00105] Aspect 7. A fluorinated polymer comprising the reaction product of a Michael addition reaction of the fluorinated compound of any one preceding aspect and a polyfunctional acrylate.

[00106] Aspect 8. A curable composition comprising the fluorinated polymer of aspect 7 and a polyfunctional acrylate. [00107] Aspect 9. The curable composition of aspect 8 further comprising a reinforcing filler.

[00108] Aspect 10. A cured product formed from the curable composition of any one of aspects 8-9.

[00109] Aspect 1 1 . The cured product of aspect 10 comprising a film having a thickness of from greater than 0 to 20 micrometers (μηι).

[00110] Aspect 12. The cured product of any one of aspects 10 and 1 1 being disposed on a substrate.

[00111] Aspect 13. The cured product of any one of aspects 10-12 having a water contact angle of at least 100^°.

[00112] Aspect 14. A method of forming a cured product, said method comprising: applying the curable composition of any one of aspects 8-9 on a substrate; and curing the curable composition on the substrate so as to form the cured product on the substrate.

[00113] It is to be understood that the appended claims are not limited to expressed and particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments which fall within the scope of the appended claims. With respect to any Markush groups relied upon herein for describing particular features or aspects of various embodiments, different, special, and/or unexpected results may be obtained from each member of the respective Markush group independent from all other Markush members. Each member of a Markush group may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims.

[00114] Further, any ranges and subranges relied upon in describing various embodiments of the present invention independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein. One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one example, a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims. In addition, with respect to the language which defines or modifies a range, such as "at least," "greater than," "less than," "no more than," and the like, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims. Finally, an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims. For example, a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

[00115] The following examples are intended to illustrate the invention and are not to be viewed in any way as limiting to the scope of the invention.

EXAMPLES

[00116] Preparation Examples 1-3

[00117] In preparation Examples 1 -3, fluorinated compounds in accordance with the invention are prepared.

[00118] Preparation Example 1 :

[00119] A fluorinated compound is prepared by reacting a carboxylic ester compound and a silicone diamine compound. In particular, the carboxylic ester compound is commercially available under the tradename Krytox® methyl ester (weight-average molecular weight of about 2,000) from E. I. du Pont de Nemours and Company of Wilmington, DE. The silicone diamine compound comprises 1 ,3-bis(3-aminopropyl)tetramethyldisiloxane.

[00120] In particular, 14.9 grams of the silicone diamine compound and 20.0 grams of 1 ,3- bistrifuloromethylbenzene are disposed in a dry three neck flask and heated to 100 °C. 20 grams of the carboxylic ester compound in 20 grams of 1 ,3-bistrifuloromethylbenzene are disposed in the flask dropwise over a 1 hour period. The contents of the flask are stirred at 100 ^<Ό for one more hour until the methyl ester group of the carboxylic ester compound is no longer detected via infrared (IR) spectroscopy. A reaction product including the fluorinated compound results. The 1 ,3-bistrifuloromethylbenzene is stripped from the reaction product after cooling to room temperature and the fluorinated compound is disposed in 1 ,3-bistrifuloromethylbenzene at a concentration of 20 wt.%, which is referred to as the final solution of Preparation Example 1 .

[00121] Preparation Example 2:

[00122] A fluorinated compound is prepared by reacting a carboxylic ester compound and a silicone diamine compound. In particular, the carboxylic ester compound is commercially available under the tradename Krytox® methyl ester (weight-average molecular weight of about 2,000) from E. I. du Pont de Nemours and Company of Wilmington, DE. The silicone diamine compound comprises aminopropyl-terminated poly(dimethyl)siloxane (viscosity at 25 °C of 10- 15 centiStokes (cSt)).

[00123] In particular, 50.4 grams of the silicone diamine compound and 20.0 grams of 1 ,3- bistrifuloromethylbenzene are disposed in a dry three neck flask and heated to 100 °C. 20 grams of the carboxylic ester compound in 20 grams of 1 ,3-bistrifuloromethylbenzene are disposed in the flask dropwise over a 1 hour period. The contents of the flask are stirred at 100 ^<C for one more hour until the methyl ester group of the carboxylic ester compound is no longer detected via infrared (IR) spectroscopy. A reaction product including the fluorinated compound results. The 1 ,3-bistrifuloromethylbenzene is stripped from the reaction product after cooling to room temperature and the fluorinated compound is disposed in 1 ,3-bistrifuloromethylbenzene at a concentration of 20 wt.% , which is referred to as the final solution of Preparation Example 2.

[00124] Preparation Example 3:

[00125] A fluorinated compound is prepared by reacting a carboxylic ester compound and a silicone diamine compound. In particular, the carboxylic ester compound is commercially available under the tradename Krytox® methyl ester (weight-average molecular weight of about 2,000) from E. I. du Pont de Nemours and Company of Wilmington, DE. The silicone diamine compound comprises aminopropyl-terminated poly(dimethyl)siloxane (viscosity at 25 °C of 20- 30 centiStokes (cSt)).

[00126] In particular, 94.8 grams of the silicone diamine compound and 20.0 grams of 1 ,3- bistrifuloromethylbenzene are disposed in a dry three neck flask and heated to 100 °C. 20 grams of the carboxylic ester compound in 20 grams of 1 ,3-bistrifuloromethylbenzene are disposed in the flask dropwise over a 1 hour period. The contents of the flask are stirred at 100 ^<C for one more hour until the methyl ester group of the carboxylic ester compound is no longer detected via infrared (IR) spectroscopy. A reaction product including the fluorinated compound results. The 1 ,3-bistrifuloromethylbenzene is stripped from the reaction product after cooling to room temperature and the fluorinated compound is disposed in 1 ,3-bistrifuloromethylbenzene at a concentration of 20 wt.% , which is referred to as the final solution of Preparation Example 3.

[00127] Examples 1-3 and Comparative Example 1 :

[00128] In Examples 1 -3, fluorinated polymers are prepared from the fluorinated compounds of Preparation Examples 1 -3, respectively. In particular, the fluorinated polymers are prepared in situ in curable compositions. Comparative Example 1 illustrates a curable composition not including such a fluorinated polymer. [00129] The following components are utilized in the curable compositions of Examples 1 -3 and Comparative Example 1 :

[00130] Polyfunctional Acrylate comprises a blend of dipentaerythritol hexxacrylate and dipentaerythritol pentaacrylate (1 :1 molar ratio), commercially available under the tradename Kayarad dPHA from Nippon Kayaku Co., Ltd. of Tokyo, Japan;

[00131] Reinforcing Filler comprises a colloidal silica mono-dispersed in isopropanol (30 wt.% S1O2), commercially available under the tradename ORGANOSILICASOL™ MEK-ST from

Nissan Chemical America Corporation of Houston, TX.

[00132] Photopolymerization Initiator comprises 1 -hydroxycyclohexyl phenyl ketone, commercially available under the tradename Irgacure® 184 from BASF Corporation of Florham Park, NJ.

[00133] Filler Treating Agent comprises 3-methacryloxypropyl trimethoxysilane.

[00134] Example 1 :

[00135] 16.3 grams of 2-butanone, 21 .3 grams of the Polyfunctional Acrylate, 2 grams of the final solution of Preparation Example 1 , and 0.49 grams of an aminopropyl-terminated poly(dimethyl)siloxane (viscosity at 25 °C of 20-30 centiStokes (cSt)) are disposed in a dry three neck flask and heated at 50 'C under stirring for 1 hour. The fluorinated compound in the final solution of Preparation Example 1 reacts in situ with a portion of the Polyfunctional Acrylate to form a fluorinated polymer in the flask. 5.3 grams of the Filler Treating Agent, 53.3 grams of the Reinforcing Filler, and 0.46 grams of deionized water are disposed in the flask while heating at 50 'C under stirring for another hour. After cooling to room temperature, 2.0 grams of the Photopolymerization Initiator are disposed in the flask to give the curable composition.

[00136] Example 2:

[00137] 16.3 grams of 2-butanone, 21 .3 grams of the Polyfunctional Acrylate, 2 grams of the final solution of Preparation Example 2, and 0.49 grams of an aminopropyl-terminated poly(dimethyl)siloxane (viscosity at 25 °C of 20-30 centiStokes (cSt)) are disposed in a dry three neck flask and heated at 50 'C under stirring for 1 hour. The fluorinated compound in the final solution of Preparation Example 2 reacts in situ with a portion of the Polyfunctional Acrylate to form a fluorinated polymer in the flask. 5.3 grams of the Filler Treating Agent, 53.3 grams of the Reinforcing Filler, and 0.46 grams of deionized water are disposed in the flask while heating at 50 'C under stirring for another hour. After cooling to room temperature, 2.0 grams of the Photopolymerization Initiator are disposed in the flask to give the curable composition. [00138] Example 3:

[00139] 16.3 grams of 2-butanone, 21 .3 grams of the Polyfunctional Acrylate, 2 grams of the final solution of Preparation Example 3, and 0.49 grams of an aminopropyl-terminated poly(dimethyl)siloxane (viscosity at 25 °C of 20-30 centiStokes (cSt)) are disposed in a dry three neck flask and heated at 50 'C under stirring for 1 hour. The fluorinated compound in the final solution of Preparation Example 3 reacts in situ with a portion of the Polyfunctional Acrylate to form a fluorinated polymer in the flask. 5.3 grams of the Filler Treating Agent, 53.3 grams of the Reinforcing Filler, and 0.46 grams of deionized water are disposed in the flask while heating at 50 'C under stirring for another hour. After cooling to room temperature, 2.0 grams of the Photopolymerization Initiator are disposed in the flask to give the curable composition.

[00140] Comparative Example 1 :

[00141] 16.3 grams of 2-butanone, 21 .3 grams of the Polyfunctional Acrylate, 5.3 grams of the Filler Treating Agent, 53.3 grams of the Reinforcing Filler, and 0.46 grams of deionized water are disposed in a dry three neck flask and heated at 50 'C under stirring for 1 hour. After cooling to room temperature, 2.0 grams of the Photopolymerization Initiator are disposed in the flask to give the curable composition. The curable composition of Comparative Example 1 does not include the fluorinated polymer formed via the Michael addition reaction between a fluorinated compound and the polyfunctional acrylate, unlike the curable compositions of Examples 1 -3.

[00142] Cured Products:

[00143] The curable compositions of Examples 1 -3 and Comparative Examples 1 are filtered via a syringe filter (polytetrafluoroethylene with glass microfiber; 30 millimeter (mm) diameter; 0.45 micrometer (μηι) pore size; commercially available under the tradename Whatman® from GE Healthcare of Little Chalfront, U.K.). Samples of the curable compositions of Examples 1 -3 and Comparative Example 1 are applied to a polycarbonate substrate. Specifically, the samples of the curable compositions are applied to the substrates via spin coating with a spin-coater (commercially available from SUSS MicroTec of Sunnvale, CA) at 200 rotations per minute (rpm) for 20 seconds and then 1 ,000 rpm for 30 seconds to provide wet films on the different substrates. The wet films are dried for 10 minutes at 70 °C and cured via UV irradiation at a dosage of 2 J/cm² for a period of time sufficient to cure the wet films and give cured products. The cured products are in the form of thin films disposed on the substrates.

[00144] Physical properties of the cured products formed from the curable compositions of Examples 1 -3 and Comparative Example 1 are measured as described below. [00145] Contact Angle:

[00146] The static contact angles of water and hexadecane on each of the cured products are evaluated. Specifically, the static contact angles of water and hexadecane are measured via a VCA Optima XE goniometer, which is commercially available from AST Products, Inc., Billerica, MA. The water contact angle measured is a static contact angle based on a 2 μΙ_ droplet on each of the cured products. The contact angle of water is referred to as WCA (water contact angle), and the contact angle of hexadecane is referred to as HCA (hexadecane contact angle). The WCA and HCA values are degrees (°).

[00147] Pencil Hardness:

[00148] The pencil hardness of each of the cured products is measured in accordance with ASTM D3363 - 04(201 1 )32, entitled "Standard Test Method for Film Hardness by Pencil Test." As understood in the art, pencil hardness values are generally based on graphite grading scales, which range from 9H (hardest value) to 9B (softest value).

[00149] Cross Hatch Adhesion Test:

The cross hatch adhesion test is performed in accordance with ASTM D 3002, entitled "Evaluation of Coatings Applied to Plastics" and ASTM D 3359-09e2, entitled "Standard Test Methods for Measuring Adhesion by Tape Test" utilizes right angle cuts (which are cross- hatched) in the cured products to the underlying substrates. The cracking of cutting edges and loss of adhesion is inspected based on the ASTM standard below:

ASTM class 5B: The cutting edges are completely smooth and none of the squares in the lattice formed from the cross hatch test are detached from the underlying substrate;

ASTM class 4B: Detachment of small flakes of the cured products at intersecting cuts; a cross cut area not significantly greater than 5% by area is affected;

ASTM Class 3B: The cured product has flaked along the cutting edges and at intersecting cuts; a cross cut area significantly greater than 5%, but not significantly greater than 15%, by area is affected;

ASTM class 2B: The cured product has flaked along the cutting edges partly or wholly in large ribbons, and/or has flaked partly or wholly on different squares in the lattice formed from the cross hatch test; a cross cut area significantly greater than 15%, but not significantly greater than 35%, by area is affected;

ASTM class 1 B: The cured product has flaked along the cutting edges in large ribbons and/or some squares in the lattice formed from the cross hatch test have detached partly or wholly from the underlying substrate; a cross cut area significantly greater than 35%, but not significantly greater than 65%, by area is affected; ASTM Class OB: Any degree of flaking that cannot be classified as ASTM class 1 B-5B.

[00150] Anti-abrasion Test:

[00151] The anti-abrasion test utilizes a reciprocating abraser - Model 5900, which is commercially available from Taber Industries of North Tonawanda, New York. The abrading material utilized is a CS-17 Wearaser® from Taber Industries. The abrading material has dimensions of 6.5 mm x 12.2 mm. The reciprocating abraser is operated for 10, 25, and 100 cycles at a speed of 25 cycles per minute with a stroke length of 1 inch and a load of 10.0 N. Following each of the cycles, the surfaces of the cured products are visually inspected to determine abrasion. The following ratings are assigned based on this optical inspection:

Rating 1 : no damage to the cured product;

Rating 2: minor scratches to the cured product;

Rating 3: moderate scratches to the cured product;

Rating 4: substrate is partially visible through the cured product; and

Rating 5: substrate is fully visible through the cured product.

[00152] Stain Marker Test:

[00153] The stain marker tests measures optically the ability of the cured products to exhibit stain resistance. In particular, in the stain marker test, a line is drawn on each of the cured products with a Super Sharpie® permanent marker (commercially available from Newell Rubbermaid Office Products of Oak Brook, IL). The lines are inspected optically to determine whether the lines beaded on the cured products. A "1 " ranking indicates that the line fully beads into a small droplet, whereas a "5" ranking indicates that the line does not bead whatsoever. Thirty seconds after drawing each line on the cured products, the line is wiped with a piece of paper (Kimtech Science™ Kimwipes™, commercially available from Kimberly-Clark Worldwide, Inc. of Irving, TX) five consecutive times. A "1 " ranking indicates that the line (or beaded portion thereof) is fully removed from the substrate, whereas a "5" ranking indicates that the line is not removed whatsoever.

[00154] Table 1 below illustrates the physical properties of each of the cured products based on the tests described above. In Table 1 , "Ex." designates Example; and "C.E." designates Comparative Example.

[00155] Table 1 :

Ex. 2 1 H 5B 2 0 103.1 58.4 1 2 3

Ex. 3 1 H 5B 2 0 104.3 60.1 1 2 3

C.E. 1 1 H 5B 5 5 84.1 28.4 1 2 4

[00156] As clearly illustrated above, the curable compositions of Examples 1 -3, which included the fluorinated polymer prepared via the Michael addition reaction between a polyfunctional acrylate and the fluorinated compounds of Preparation Examples 1 -3, respectively, formed cured products having excellent physical properties, particularly as compared to the cured product formed from the curable composition of Comparative Example 1 , which did not include any such fluorinated polymers.

[00157] The invention has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the present invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described.

Claims

CLAIMS What is claimed is:

1 . A fluorinated compound having the general formula (1 ):

Rf-CONR-(CH2)_a-SiR¹ X-(OSiR¹ X)_b-(CH₂)c-Y (1 );

wherein Rf is a fluoro-substituted group; R is H or a substituted or unsubstituted hydrocarbyl group; each R¹ is an independently selected substituted or unsubstituted hydrocarbyl group; each X is independently R¹ or an amine-containing group; Y is a terminal group selected from R and X; subscripts a and c are each are each independently selected from 0 and an integer from 1 to 10; and subscript b is an integer from 2 to 20; with the proviso that said fluorinated compound includes at least one amine-containing group designated by X or Y.

2. The fluorinated compound of claim 1 wherein R is H such that said fluorinated compound has the general formula (2):

Rf-CONH-(CH₂)_a- SiR¹ X-(OSiR¹ X)_b-(CH₂)_c-Y (2);

wherein Rf, R¹ , X, Y, and subscripts a, b, and c are as defined in claim 1 .

3. The fluorinated compound of claim 2 wherein X is and Y is an amine-containing group such that said fluorinated compound has the general formula (3):

Rf-CONH-(CH₂)_a- SiR¹ ₂-(OSiR¹ ₂)_b-(CH₂)_c-NHR (3);

wherein Rf, R, R¹ , and subscripts a, b, and c are as defined in claim 1 .

4. The fluorinated compound of claim 3 wherein subscripts a and c are each 0 such that said fluorinated compound has the general formula (4):

Rf-CONH- SiR¹ ₂-(OSiR¹ ₂)b-NHR (4);

wherein Rf, R, R¹ , and subscript b are as defined in claim 1 .

5. The fluorinated compound of any one preceding claim wherein Rf: (i) is partially fluorinated; (ii) comprises a perfluoropolyether segment; or (iii) both (i) and (ii).

6. The fluorinated compound of claim 5 wherein Rf comprises said perfluoropolyether segment, said perfluoropolyether segment comprising moieties of general formula (5): -(C3 60)x-(C2F₄0)_y-(CF2)z- (5);

wherein subscripts x, y, and z are each independently selected from 0 and an integer from 1 to 40, with the proviso that x, y, and z are not simultaneously 0.

7. A fluorinated polymer comprising the reaction product of a Michael addition reaction of the fluorinated compound of any one preceding claim and a polyfunctional acrylate.

8. A curable composition comprising the fluorinated polymer of claim 7 and a polyfunctional acrylate.

9. The curable composition of claim 8 further comprising a reinforcing filler.

10. A cured product formed from the curable composition of any one of claims 8-9.

1 1 . The cured product of claim 10 comprising a film having a thickness of from greater than 0 to 20 micrometers (μηι).

12. The cured product of any one of claims 10 and 1 1 disposed on a substrate.

13. The cured product of any one of claims 10-12 having a water contact angle of at least 100^°.

14. A method of forming a cured product, said method comprising:

applying the curable composition of any one of claims 8-9 on a substrate; and

curing the curable composition on the substrate so as to form the cured product on the substrate.