MXPA98001888A - Coatings containing fluora esters - Google Patents

Abstract

The coating compositions containing an alkyl, urethane or unsaturated polyester resin, and an unsaturated acid ester and a fluorinated alcohol, wherein the cured coating has a contact angle for the hexadecane increased by at least about 40 degrees and the water and oil repellency improved durab

Description

COATINGS CONTAINING FLUORITE ESTERS FIELD OF THE INVENTION This invention relates to coating compositions containing fluorinated esters of more saturated carboxylic acids that provide durable water and oil repellent surfaces for the cured coating, and cured coatings are derived from said compositions.

BACKGROUND OF THE INVENTION The inventive coating compositions in the present invention are the alkyd coating compositions, Type I urethane coating compositions, and coating coatings in a hydrated polystyrene, typically a paint, clear coating, or REF: 26848 dye. All coating compositions listed above after drying or curing show low contact angles for hexadecane, are easily wetted by the oil, and are susceptible to the effect by the soil. Coating compositions are described in Outlines of Paint Technology, Halstead Press, New York, Third Edition, 1990) and Surface Coatings Vol. I, Raw Materials and Their Usage (Chapman and Hall, New York, NY, Second Edition, 1984) . A common factor in these compositions for recovery is an unsaturated resin or prepolymer structure that allows the polymerization of olefinic groups in the main chain or side chain.

Conventional alkyd coatings use, as the binder or film-forming compound, an alkyd resin for drying or curing. The compositions for alkyd resin coating contain unsaturated aliphatic acid residues derived from the drying oils. These resins spontaneously polymerize in the presence of oxygen or air to produce a solid protective film. The polymerization is called "drying" or "curing" and occurs as a result of the oxidation of the non-unsaturated or unsaturated bonds in the aliphatic acid compound of the oil by the atmospheric oxygen. When applied to a surface as a thin liquid layer of formulated alkyd coating, the cured films they form are relatively hard, not melted, and substantially insoluble in many organic solvents that act as solvents or diluents for the non-oxidized alkyd resin or drying oil . Said drying oils have been used as raw materials for oil-based coatings and are described in the literature.

Urethane coatings are classified by ASTM D-1 into 5 categories. Type I urethane coatings contain a self-hardening binder, as described in Surface Coatings Vol. I, previously cited. Type I urethane binders, also called urethane oils, oil-modified polyurethanes, or urethane alkyd, are the largest volume category of polyurethane coatings, and include typical paints, clear coatings, or dyes. Urethane coatings typically contain the reaction product of a polyisocyanate, usually toluene diisocyanate, and an ester of the polyhydric alcohol of the drying oil acids. The cured coating is formed by air oxidation and polymerization of the unsaturated drying oil residue in the binder.

Unsaturated polyester resins contain, as the unsaturated prepolymer, the product obtained from the condensation polymerization of a glycol such as 1, 2 -pr op i 1 e ng 1 i co 1 or 1, 3 -bu ti 1 eng 1 i co 1 with an unsaturated acid such as maleic (or maleic and a saturated acid, for example, phthalic) in the form of anhydrides. The unsaturated prepolymer is a linear polymer containing unsaturation in the chain. This is dissolved in an appropriate monomer, for example styrene, to produce the final resin. The film is produced by copolymerization of the polymer or linear monomer by means of a free radical mechanism. Free radicals can be generated by heat, or more usually by the addition of a peroxide, such as benzoyl peroxide, separately packaged and added before use. Said coating compositions are often called "gel coat" finishes. For the curing to take place at room temperature the decomposition of peroxides in free radicals is catalyzed by certain metal ions, usually cobalt. The peroxide and cobalt compound solutions are added separately to the mixture and stirred well before application. Also unsaturated polyester resins that are cured by a free radical mechanism are suitable for curing by irradiation, using, for example, ultraviolet light. This form of cure, in which no heat is produced, is particularly suitable for wood or board films. Other sources of radiation are also used, for example electron beam curing.

Certain fluorinated materials are known to provide oil repellency for substrates such as textiles and carpets. For example, perfluoroalkyl iodides sequentially have been converted to iodides of perf 1 uoroa 1 qui 1 eti 1 o, to alcohols of perf 1 uoroa 1 qu i 1 eti 1 o, to monomers and finally to polymers for application to said substrates.

It is known to use esters of the fluoroalkyl alcohol of the alkanoic acids generally as lubrication aids. For example, the ester of pe r f 1 u or r 1 a 1 i t of stearic acid (acid or c a t a c t co) has been used to impart repellency and lubricity to various plastics. Also, Nishihara et al. , JP308469 (1989) describes the preparation of the esters of the aliphatic carboxylic acid of various fluorinated alcohols in general as lubricants and their use as lubricants for a thin film magnetic recording medium of ferromagnetic metal. By adding the stearate of perf 1 uoroa 1 qu i 1 oeti 1 o, an ester of the fluoroalkyl ethanol of a saturated vegetable oil, for example, to the alkyd, urethane or unsaturated polyester coatings in appropriate formulations, however, no They provide water and oil repellency. Since the fluorinated compound is saturated, it chemically does not bind with the cured polymer. Therefore, oil repellency is not durable and easily lost when the surface is washed or even cleaned. According to the durable oil repellency and durable raised hexadecane contact angles are meant that the surface properties of the cured coatings are preserved by cleaning the next surface.

Certain esters of p e r f 1 u or r 1 a 1 that do not react with enamel binders have been listed by Deibig et al. in the Germán patent DE 28 21 495 C2 and includes the b i s (p e r f 1 uo r o h e x i 1 e t i 1) ma 1 e a t o. The esters of the b i s (p e r f 1 uo r 1 a 1 i i t i 1) ma 1 e a t o lead similarly to stearyl esters and do not show durable oil repellency after washing. Probably the double bond in the ester is sufficiently deactivated by 2 ester groups of 1 to 1 to 1 to 1 immediately adjacent and is not sufficiently incorporated into the binder to provide durable oil repellency.

It is highly desirable to be able to provide an effective cost and oil repellency resistant to washing to alkyd coatings, Type I urethane coatings, and unsaturated polyester coatings. The present invention provides said compositions.

BRIEF DESCRIPTION OF THE INVENTION The present invention comprises a coating composition comprising A. An ester of an unsaturated acid and a fluorinated alcohol or thiol selected from the group consisting of the formula la, Ib and 2 as follows: R £ -X-A-OC-R, Formula Rf-X-A-OC-R-Rx-CO-A-X-Rf, Fó rmu the Ib Formula 2 where Rf is a C2-C2al perfluoroalkyl radical. or a C5-C38 perfluoroalkyl radical having at least one ether oxygen atom; R is a C3-C2i unsaturated aliphatic hydrocarbon radical, a C8-Ci3 aryl radical having at least one non-aromatic double bond, or mixtures thereof; X is independently - (CH2 CON (Ri) R S02N (R :) R 2 - or - (OCH 2 CH R 3) b O -, wherein m is 1 to about 20, b is 3 to about 15; Ri is H or alkyl radical of 1 to about 4 carbon atoms, R 2 is C 1 -C 12 alkylene, and R 3 is H or C H 2 C 1; A e s O or S; R x is a divalent C 3 -C 22 unsaturated aliphatic hydrocarbon radical; a divalent C 8 -C n aryl radical having at least one non-aromatic double bond, or mixtures thereof; is B. an alkyd, Type I urethane or unsaturated polyester resin; wherein a cured coating resulting from said coating composition has a contact angle for the hexadecane increased by at least about 40 degrees.

In addition, the present invention comprises coating compositions defined above in a dry or cured state.

Furthermore, the present invention comprises an improvement method for oil repellency and water repellency of an alkyd, urethane or unsaturated polyester coating composition comprising the addition to said composition for coating an ester defined above.

Furthermore, the present invention comprises an ester of perfluoroalkyl alkenoate having the structure Rf-X-0-CO-R e where 0-CO-R is a residue of the C10-C: 4 alkenoic acid containing at least 2 double bonds; X is a divalent radical containing 1-20 atoms in the chain; Y R £ is a C-C2o perfluoroalkyl group selected from the group consisting of Rf-S02 (Et) -CH2CH2 Rf-S02N (Me) -CH2CH2 Rf-S02N (Bu) -CH2CH2 DETAILED DESCRIPTION OF THE INVENTION This invention comprises coating compositions containing an unsaturated alkyd, urethane or polyester resin and an ester of an unsaturated acid and a fluorinated alcohol or thiol, wherein a cured coating resulting from said coating composition has a contact angle for the hexadecane increased by at least about 40 degrees.

By the term "urethane coating", it is used after, means a conventional liquid coating based on Type I urethane resins that contain a binder or ox i dab 1 e, typically a paint, clear coating, or dye. Urethane coatings typically contain the reaction product of a polyisocyanate, usually toluene diisocyanate, and an ester of the polyhydric alcohol of the drying oil acids. The cured coating is formed by air oxidation and polymerization of an unsaturated drying oil residue in the binder.

By the term "unsaturated polyester coating", as used below, it means a conventional liquid coating based on unsaturated polyester resins, it is dissolved in monomers and containing initiators and catalysts as necessary, typically as a paint formulation, of Clear coating, or gel coat. The resin contains as the unsaturated prepolymer the product obtained from the condensation polymerization of a glycol with an unsaturated acid in the form of anhydrides. The prepolymer is a linear polymer that contains unsaturation in the chain and is dissolved in an appropriate monomer to produce the resin. A cured coating is produced by copolymerization of the linear polymer or monomer by means of a free radical mechanism.

By the term "coating composition", as used herein, it means a liquid formulation of alkyd resin, Type I urethane, or unsaturated polyester, applied to a substrate. It includes paints, varnishes, finishes, enamels, dyes and similar materials.

By the term "cured coating" as used herein means the final protection and / or decoration film obtained after the volatile compounds of a coating composition have evaporated and the polymerizations associated with the curing process are completed. .

The ester of an unsaturated acid and a fluorinated alcohol or thiol used in the coating compositions, cured coating compositions, and method of this invention has the formula Ia, Ib, or 2 as previously defined.

More particularly, in the formula la, Ib, and 2, Rf is selected from the group consisting of (a), (b), and (c) as follows: (a) F, (CF2) n- wherein n is 2 to about 20; (b) CF3-CF-O- (CF2) e- wherein e is 1 to CF3 about 5; Y (c) wherein g is 1 to about 6, and h is about 3 to about 10.

The preferred examples of Rf-X- include the following: From the definition (a) of Rf: 1) F (CF2) n (CH2) m-, where n is 2 to about 20 and m is 1 to about 20; 2) F (CF2) n-CON (Ri) R2-, where n, Ri and R2 are as previously defined; 3) F (CF2) n-S02 (Ri) R2-. where n, Ri and R2 are as previously defined; 4) F (CF2) n- (OCH2CHR3) d0-, wherein n, R3 and d are as previously defined; Y from the definition (b) of R F C 3 F-O-ÍF2CF2) -. { CH2) - FjC 'e m where e and m are as previously defined from the definition (c) of R, 1) F (CF2) g-0- (CF-CF2-0-) h-CF- (CH2 > m I I CF3 CF3 where g, h and m are as previously defined The esters of the unsaturated carboxylic acids and the fluorinated alcohols or thiols are useful as compounds of the coating compositions of the present invention. The coating compositions of the present invention are useful for providing a decorative and / or protective coating for a wide variety of substrates. Such substrates include first the construction materials and hard surfaces such as wood, metal, sheet elements for walls, masonry materials, concrete, fiber board, paper and other materials. In the application, said coating compositions are cured by conventional methods, and the cured coatings of the present invention exhibit several valuable properties. Specifically, the cured coatings of this invention, compared to conventional cured coatings, exhibit improved anti-blockage properties, and improved water and oil repellency and durability thereof, as demonstrated by contact angle measurements. The results of improved water and oil repellency result from improved soil resistance and improved surface coverage of the cured coating. The unsaturated fluorinated esters preferably migrate to the surface of the coating of the present invention, and, to the cured resin of the coating, the ultimate property provides durability for improved water and oil repellency. By durable increased hexadecane contact angles and durable oil repellency means that the advantageous surface properties of the cured coatings of the present invention are preserved by following several simulations of surface cleaning. Therefore, the oil and water repellency and the impurity are preserved after conventional washing of the surface.

The coating compositions of this invention contain a mixture of an alkyd resin, Type I urethane or unsaturated polyester and sufficient fluorinated esters of the unsaturated carboxylic acids of the above structures such that the coating composition contains 50-10,000 μg / g. by weight of fluoro, and preferably 150-10,000 μg / g of fluoro, in the volatile content of the composition. The cured coating of this invention resulting from said composition has a contact angle for the hexadecane increased durable of not less than 40 degrees and a contact angle for the durable diminished hexadecane of not less than 20 degrees.

The contact angle formed between a surface and a drop of liquid is a measure of the wettability or repellency of the surface for the liquid. A wettable surface has low contact angles close to zero degrees, a repellent surface has higher contact angles. Therefore the contact angle formed by an oily liquid such as hexadecane is widely used as a measure of the oil repellency of a surface. In general, the contact angles for the hexadecane indicate that a surface has greater resistance and dirt and soil repellency, and is easier to apply.

The fluorinated esters of the unsaturated carboxylic acids used in the compositions and method of this invention are prepared by conventional processes for the synthesis of the esters. These processes include the direct esterification of unsaturated acids with fluorinated alcohol (for example a perfluoroalkyl ethanol) or thiol, or the transesterification between the fluorinated alcohol or thiol and esters of the unsaturated acids) for example the glycerol esters comprising a drying oil or the methyl esters of the drying oil acids). The degree of incorporation of the fluorinated alcohol or thiol can be maximized by using a molar excess of the unsaturated acid during esterification or of the unsaturated ester during esterification.

The unsaturated acids required are commercially available. For example, the acids in the drying oil are obtained from natural vegetable oils. The acids are obtained in the free acid form from the oils by hydrolysis or saponification, or in the methyl ester form by methanolysis. The proportion of various acids is well known. Other unsaturated acids used in the process are easily available commercially.

The fluorinated esters of the unsaturated carboxylic acids used in the compositions and method of this invention are made from the individual fluorinated acids or mixtures thereof, and individual fluorinated alcohols or mixtures of the same individual fluorinated thiols mixtures thereof.

A number of fluorinated alcohols is commercially available, and some are listed below. Various perfluoroalkyl ethanols and derivatives are available as intermediates of F 1 or r or t e 1 orne ZONYL from E. I. du Pont de Nemours and Company, Wilmington DE. The "ZONYL" BA contains the alpha-fluoro-ome ga - (2 - hi dr oxieti 1) -po 1 i (di f 1 uo r orne ti 1 eno) in the form of a mixture of the compounds of the homologous series of the formula: F (CF2CF2) "(CH2CH2) OH, Where the values of n are shown in Table 2 below in the section marked "Materials".

Other perfluoroalkyl alcohols can be used in the present invention, such as the sulfonamide of 1-perfluoroalkyl, available from Dainippon Ink and Chemicals Inc., DIC Building, Nihonbashi 7-20 3-chome, Chuo-ku , Tokyo 103, Japan. Also suitable are fluorinated diols, prepared by the process of U.S. Pat. 4,946,992 and the fluorinated thiols prepared as U.S. Pat. 3,544,663, in particular to Example 1 here.

The fluorinated esters of the unsaturated carboxylic acids are incorporated into conventional curable coating compositions at concentrations sufficient to give a cured coating containing from about 50 to about 10,000 μg / g by weight of fluoro and preferably from 150 to 5,000 μg / g. of fluoro based on the non-volatile content of the coating composition.

The increased contact angle for the durable hexadecane of the angry composition is equal to or greater than 60 degrees. The decreased contact angle for the durable hexadecane for the cured composition is equal to or greater than 20 degrees, preferably equal to or greater than 40 degrees.

The method of the present invention for providing water repellency and oil repellency of an alkyd, urethane Type-I, or unsaturated polyester coating composition comprises incorporating into said coating compositions the fluororested esters previously described in unsaturated carboxylic acid and the fluorinated alcohol or thiol. The esters are added in a melt condition or after dissolution in a compatible solvent. The melt or solution provides a method to ensure that the fluorinated esters are easily and completely mixed in the coating composition. Alternatively, the reaction mixture in which the esters are synthesized can be used, without the isolation of the esters, the solvents of any given reaction are chosen to be suitable for the final coating composition and the reaction product is heated to ensure the homogeneity Examples of solvents compatible with the compounds of the coating compositions of this invention are mineral spirits, deodized mineral spirits, Stoddard solvent, and other solvents compatible with the specific coating and coating composition.

To prepare the coating compositions of the present invention containing an alkyd resin, the fluorinated esters are heated to about 90 ° C with stirring until a homogeneous and completely melted mixture is obtained. The hot liquid is poured into the alkyd coating composition and stirred to a homogeneous mixture. Alternative and, the hot fluorinated esters are dissolved in an appropriate solvent compatible with the alkyd coating composition, such as the Stoddard solvent, and subsequently the solution of the fluorinated esters is added to the alkyd coating compositions. The preparation of the compositions for coating of the present invention containing the Type I urethanes and a fluorinated ester as previously described is carried out as described above for the coating compositions containing alkyd resins. The preparation of the coating compositions of the present invention containing unsaturated polyesters and the fluorinated ester previously described is carried out as described above for the coating compositions containing an alkyd resin, with the addition of the fluorinated esters which is made to the alkyd / styrene resin mixture.

The methods of application of the coating compositions for surfaces, and the drying properties of the coating compositions are essentially not affected by the addition of the fluorinated esters of the unsaturated carboxylic acids.

Although not intended to be determined by theory, it is believed that the mechanism of generating the advantageous properties of the cured composition of this invention is via binding of the fluorinated esters in the coating during curing. It is believed that the fluorinated esters of the unsaturated carboxylic acids used in this invention, when applied to a surface as part of a liquid coating composition, migrate to the surface for coating before curing, becoming concentrated on the surface, and chemically they bind in the coating during curing, thus providing durable water and oil repellency for the cured composition.

When the repellent surfaces that result from an oriented surface of the surface, including the surfaces of the coatings of this invention, are frequently subjected to reversible "inversion" with prolonged exposure to water or aqueous solutions. Water repellency returns after desiccation. TEST METHODS Method 1.- Measurements of the contact angle.

The contact angles were measured by the Sésil Drop Method which is described in A. W. Adamson "The Physical Chemistry of Surfaces", 15a. Edition, Wiley & Sons, New York, 1990. Additional information on the equipment and procedure for the measurement of contact angles is provided by R. H. Dettre et al. In "Wettability", Ed. By J. C. Berg, Marcel Dekker, New York, 1993.

In the Sésil Drop Method, a Rame-Hart optical bank available from Rame-Hart Inc., Bloomfield Avenue 43, Mountain Lakes, NJ, is used to hold the substrate in the horizontal position. The contact angle is measured at a prescribed temperature with a telescopic goniometer from the same manufacturer. A drop of test liquid is placed on the surface and the tangent is precisely determined at the point of contact between the drop and the surface. An increased angle is determined by the increase in the size of the liquid drop and the decreased angle is determined by the decrease in the size of the liquid drop. The data is typically presented as decreased and increased contact angles.

The relationship between the contact angles of the organic liquid and the water, and the impurity and the retention of dirt from surfaces is described in A. W. Adamson, supra. In general, the greater contact angles for the hexadecane are indicative that a surface has greater strength and repellency to dirt and soil, and easier to implove the surface.

Due to the durable oil repellency and the increased and decreased contact angles for the hexadecane it means that the advantageous surface properties of the modified cured coatings of the present invention are retained following surface cleanliness. The increased and decreased contact angles for Hecadecan and water of the coating compositions of the present invention were measured in the form of coatings with wash test panels, matte black P-121-10N Leneta 6.5 x 17 inches (16.5 x 43.2 cm) by Lenta Comany, Mahwah, NJ. The coating compositions were prepared as described above with the fluoroester added in an amount to give a concentration of fluoro μg / g in the mixed product. The fluoroester containing the coating composition is applied to the Leneta test panel using a forward advancing angle of the film of 7 mil (0.18 mm). The test panel is attached to a Gardco DP-1218L Leveling Descent Plate (Paul N. Gardner Co., Pompano Beach FL) and cleaned before sweeping with a cotton swab damp with isopropyl alcohol. . The coated panel is typically cured for 7 days at room temperature conditions prior to testing.

Method 2 - Durability of Washing with Detergent The wash durability of the fluoroester containing the coating composition for surface cleaning is determined using a DIO Garment Model use and wash tester (Paul N. Gardner Co., Pompano Beach FL) and an abrasion vessel WA-2225 Gardco. A 6.5 x 1 inch (16.5 x 2.5 cm) test strip cut from the coated Leneta test panel is positioned on the test sample tray and secured to it with a 3/4 inch (1.9 cm) transparent tape in width such that approximately a 2 x 3/4 inch (5.1 x 1.9 cm) portion of the coated test panel should be washed. The base plate of the abrasion boat is covered with a piece of 9 x 9 inches (22.9 x 22.9 cm) of bleached white cotton 20b Idealfold from Royal Textiles available from DeRotal Textiles, Camden, SC. The cotton cheesecloth is folded perpendicular to the joint in half and half again and is fastened to the base plate such that the surface wash layers are joined together freely. The cheesecloth pad is moistened with 20 ml of a 1% aqueous Tide detergent solution (Proctor and Gamble Co., Cincinnati, OH) before the test band is washed. The test band is removed after 10 wash cycles, washed free of the Tide solution with water and dry air one day before the increased contact angles for the hexadecane decreased on the washed surface are measured.

Method 3 - Antiblock Test ASTM 4946-89 provides a method for measuring the anti-blocking (unfixed) properties of surface coatings. The painted surfaces of the flat panels are placed phase-to-phase. A No. 8 pusher is placed on top of the pair, and a weight of 1000 g is placed on top of the pusher, creating a pressure of 1.8 psi (12.4 kPa). The heavy pair is maintained for 30 minutes at 120 +/- 5 ° F (49 +/- 3 ° C), then cooled to room temperature for 30 minutes. Then the samples are peeled and the stickiness estimate is noted. The blocking resistance is assessed according to Table 1 below: TABLE 1 Estimates of the Antiblock Test based on ASTM 4946-89 The general procedure of ASTM 4946-89 is used to measure the anti-blocking properties of the coating compositions of this invention as a function of days of cure. The measurements are made using cut sections of 1.5 x 1.5 inches (3.8 x 3.8 cm) of the coated Leneta wash test panels prepared as described above.

MATERIALS The following materials are used in the following examples unless otherwise indicated.

A. Paintings 1) INPERVO (TM) White High Alkyl Enamel Paint by Benjamin Moore and Comapny, Montvale, NJ 07645 2) Enterprise Shine Polyurethane, from Valspar Corporation, Wheeling, Illinois 60090 3) Oil Base Paint with Exterior Gloss SWP (white), from S erwin-Williams Company, Cleveland, Ohio 44101 4) Duron Outdoor Alkyd House Paint (white), by Duron, Inc., Bettsville, MD 20705 ) Neutral Gel Layer, from Fiber Glast Developments Corporation, Neva Street 1994, Daiton, Ohio 45414 6) Neste Gel Coat WG30001S, from Neste Polyester Inc., 5106 Wheeler Avenue, Fort Smith, Arkansas 72901 B. Alcohols and Fluorinated Thiols 1) Intermediates of Fl oo r o t 1 orne r ZONYL BA and ZONYL BA-N of the formula F (CF2CF2) nCH2CH2OH, of E. I. du Pont de Nemours and Company, Wilmington DE, homologous composition shown in Table 2 TABLE 2 Homologous composition for ZONYL BA and ZONYL BA-N Percent in Weight of the Homologous Value of n ZONYL BA ZONYL BA-N 3 27 37 0 3 4 28 32 45 52 5 14 20 26 32 6 13 10 14 7 3 6 2 5 0 2 0 2 0 1 0 1 2) N-methyl-Neonate Sulfonamide 1 pe rf 1 uo roocta no, FX-42, Dainippon Ink and Chemicals, Inc., DIC Building, 7-20, Nihonbashi 3-chome, Chuo-ku, Tokyo 103 , Japan. 3) The glycols of the neopentyl bis- (perf 1 uo roa 1 qu i 1 eti lme r r cap) of the formula [F (CF2CF) nCH2CH2SCH2] 2C (CH2OH) 2, where n is 3 to 8, preferably 3, 4 and 5, are prepared by the method of US Pat. No. 4,946,992. 4) The thiols of pe rf 1 uo roa 1 qu i 1 eti 1 o of the formula F [C F2 C F2] n CH2 CH2-S-H, where n is 4 to 7, are prepared by the procedure of Example 1 of the US Patent 3,544,663.

Unsaturated Acids 1) Flaxseed Fatty Acid Emery 644, from Henkel Corporation, Emery Group, Northlake Street 11501, Cincinnati, Ohio 45249 2) TRLA-50 Flaxseed Fatty Acid, from Twin Rivers Technologies Inc., Washington Street 780, Quinci, Ma s s a c hu s s t t s, 02169 3) Fatty Acid Flaxseed Industrene 120, from Witco Corporation, Humko Chemical Division, An American Line, Greenwich, CT 06831 4) Emery 618 Soybean Fatty Acid, from Henkel Corporation, Emery Group, Northlake Street 11501, Cincinnati, Ohio, 45249 5) Emersol 315 Linoleic Acid, from Henkel Corporation, Emery Group, Northlake Street 11501, Cincinnati, Ohio, 45294 6) Linoleic Acid, 99% plus, from Aldrich Chemical Company, Inc., San Pablo Oester Avenue 1001, Milwaukee, Wl 53233 7) Cañola R-910 Fatty Acid, from Proctor and Gamble, Chemicals Division, Zip Code 599, Cincinnati, Ohio 45201 8) Oleic acid, 99 plus%, from Aldrich Chemical Company, Inc., San Pablo Avenue west 1001, Miwawakee, WL 53233 9) Methyl ester of Tung oil, from RTD Chemical Corporation, 1500 Rte. 527, Suite 305, Hacke t ts town, N. J. 07840 ) Oil acids type SAFACID UDF, from Pronova O 1 eo ch emi ca 1 s as, Framnesvein 54, Postal code 2051, Hasle, N-3202 Sandefjord, Norway 11) Oil acids type SAFACID U, from Pronova 01 eo ch emi ca 1 s as, Framnesvein 54, Postcode 2051, Hasle, N-3202 Sandefjord, Norway 12) Ethyl Sorbate, 99%, from Fisher Scientific, Acros Organics, Forbes Avenue 711, Pittsburgh PA 15219 13) Acid 2, 4 - hex adi n e n c y, 99% (sorbic acid), from Fisher Scientific, Acros Organics, Forbes Avenue 711, Pittsburgh PA 15219 14) Cinnamic Trans Acid, from Fisher Scientific, Acros Organics, Forbes Avenue 711, Pittsburgh PA 15219 ) D ime t i i t a con a t, 97%, from Aldrich Chemical Company, Inc., Avenida San Pablo Oeste 1001, Milwaukee, Wl 53233 16) Itaconic Acid, 99 plus%, from Aldrich Chemical Company, Inc., St. Paul West Avenue 1001, milwaukee, Wl 53233 17) 2-oct anhydride ade cen-1-i 1 succinic, from Humphrey Chemical Company, Inc., Devine Street 45, North Haven, CT 06473 18) Anhydride of 2-do of c-n-1-i 1 s c c i n i, 97%, of Aldrich Chemical Company, Inc., St Paul Avenue West 1001, Milwaukee Wl 53233 D. Saturated acids 1) Stearic acid, 90%, from Sigma Chemical Company, Zip Code 14508, San Luis, Mo. catalysts 1) Phosphorous Acid, by Albright & Wilson Americas, Zip Code 26299, Richmond, VA 23229 2) titanate of t e t r a i s op r op i 1 or TIZOR TPT, from E. I. du Pont de Nemours and Company, Wilmington DE EXAMPLES Ejeinplo 1 To a 250 ml 4-necked round-bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet 1 is loaded with 56.07 g of Flaxseed Fatty Acid Emery 644, 75.84 g of Fluorotelomer intermediary ZONYL BA and 0.17 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C for about 45 hours to produce the fluorinated ester, at which time the mixture contains 0.05% residual ZONYL BA by gas chromatographic analysis (GC) and 37.9% fluoro by the combustion analysis.

E j emp lo 2 To a 1000 ml 4-necked round-bottomed flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet is loaded with 420 g of Flaxseed Fatty Acid TRLA-50, 566 g of Fluorotelomer intermediate ZONYL BA and 0.65 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C for about 24.5 hours to produce the fluorinated ester, at which time the mixture contains 0.18% of the ZONYL BA residual by GC analysis and 38.2% fluoro by combustion analysis.

E j emp lo 3 To a 250 ml 4-necked round-bottomed flask, adapted with a mechanical stirrer, a temperature control device, a Dean-ark trap, a condenser, and a nitrogen inlet, is charged with 56.07 g of Fatty Acid of Industrene Flaxseed 120, 75.84 g of Fluorotelomer intermediary ZONYL BA and 0.17 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C for about 25 hours to produce the fluorinated ester, at which time the mixture contains 0.07% residual ZONYL BA by GC analysis and 37.9% fluoro by combustion analysis.

T h e 4 A 1000 ml 4-necked round bottom flask, equipped with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a 1/2-in. of nitrogen is charged with 210.39 g of Emery 618 Soybean Fatty Acid, 302.70 g of the Fluorotelomer intermediate ZONYL BA and 0.37 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C for about 24 hours to produce the fluorinated ester, at which time the mixture contains 0.30% residual ZONYL BA by GC analysis and 37.8% fluoro by combustion analysis.

E j emp lo 5 To a 250 ml 4-necked round-bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet 1 is loaded with 56.58 g of Emersol 315 Linoleic Acid, 76.97 g of Fluorotelomer intermediate ZONYL BA and 0.13 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C for about 45 hours to produce the fluorinated ester, at which time the mixture contains 0.09% of the ZONYL BA by GC analysis and 38.5% of fluoro by the combustion analysis.

E j emp lo 6 To a 100 ml 4-necked round bottom flask equipped with a mechanical stirrer, a temperature control device, a short path distillation head, a condenser, a receiver and a triad / sa 1 i da of nitrogen is charged with 24.96 g of linoleic acid, 99% plus, 42.26 g of Fluorotelomer intermediate ZONYL BA and 0.12 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at approximately 145 ° C for approximately 45 hours at which time it contains 0.04% residual ZONYL BA by GC analysis and 42.2% fluoro by combustion analysis. The products of esters having the following molecular weights are identified by the gas chromatographic analysis of the gas mixture as a mixture of the reaction mixture and gas chromatography (GC / MS).

R n 2 3 4 5 6 7 8 17 H 3 526 626 726 826 926 1026 1126 R and n are as previously defined E j emp lo 7 To a 250 ml 4-necked round-bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet 1 is loaded with 106.29 g of Cañóla Fatty Acid R-910, 144.22 g of Fluorotelomer intermediate ZONYL BA and 0.19 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C for about 44 hours to produce the fluorinated ester, at which time the mixture contains 0.04% residual ZONYL BA by GC analysis and 38.3% fluoro by combinatorial analysis.

EXAMPLE 8 To a 100 ml 3-necked round bottom flask equipped with a mechanical stirrer, a temperature control device, a short path distillation head, a condenser, a receiver and an inlet 1 Nitrogen is charged with 25.50 g of oleic acid, 99% plus, 42.88 g of Fluorotelomer intermediate ZONYL BA and 0.13 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at approximately 145 ° C for approximately 26 hours to produce the fluorinated ester, at which time the mixture contains 0.10% residual ZONYL BA by GC analysis and 41.6% fluoro by combustion analysis.

E j emp lo 9 To a 250 ml 4-necked round-bottomed flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inflow is charged with nitrogen. 58.38 g of methyl esters of tung oil, and 86.61 g of Fluorotelomer intermediary ZONYL BA. The mixture is heated to and maintained at about 150 ° C for about 40 hours, with the addition of 0.4940, 0.5497, 0.4976, and 0.4735 g of the tetrais op r op i 1 titanate or TPT TIZOR at about 0.2, 4 and 23 hours elapsed, respectively, at which time it contains 2.33% of residual ZONYL BA by GC analysis and 41.1% of fluoro by combustion analysis. The ester products having the following molecular weights are identified by GC / MS analysis as compounds of the reaction mixture.

R 3 4 5 6 7 C 1 5 H 3 P 602 702 802 902 1002 C 1 7 H 3 5 * 630 730 830 930 1030 C 17 H 33 628 728 828 928 1028 C! H31 626 726 826 926 C 1? H 29 624 724 824 924 1024 R and n are as previously defined. * In addition these saturated esters, derived from saturated acid compounds, are presented.

T h e 10 To a 250 ml 4-necked round-bottomed flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a 1/2-in. Nitrogen is charged with 59.61 g of UFF-type oil acids SAFACID (acid number 188), 76.98 g of Fluorotelomer intermediate ZONYL BA and 0.15 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at approximately 145 ° C for approximately 28 hours at which time it contains 0.6% residual ZONYL BA by GC analysis and 37.91% fluoro by combustion analysis. The ester products having the following molecular weights are identified by GC / MS analysis as compounds of the reaction mixture. 3 4 5 6 7 8 13 H27 * 574 674 774 874 974 C15H37 * 602 702 802 902 1002 C 15 H 29 600 700 800 900 C 17 H 33 628 728 828 928 1028 1 C 17 H 31 626 726 C i 3 H 37 656 756 56 956 1056 C i 9 H 29 648 748 48 948 1048 C 21 H i 684 784 84 984 1084 C 2 i H 3 i 674 774 74 974 1074 R and n are as previously defined. * In addition these saturated esters, derived from saturated acid compounds, are presented.

E j a lo 11 To a 250 ml 4-necked round bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet 1 of nitrogen is charged with 62.01 g of U-type oil SAFACID (acid number 181), 76.94 g of Fluorotelomer intermediate ZONYL BA and 0.27 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at approximately 145 ° C for approximately 25 hours, at which time it contains approximately 0.5% of residual ZONYL BA by GC analysis and 36.6% of fluoro by combustion analysis. The ester products having the following molecular weights are identified by GC / MS analysis as compounds of the reaction mixture. n 3 4 5 6 7 8 C11H23 * 546 646 746 846 946 1046 C13H27 * 574 674 774 874 974 1074 C15H31 * 602 702 802 902 1002 C 15H29 600 700 800 900 «C 17 H 33 628 728 828 928 1028 C 17 H 31 626 726 826 C 19 H 37 656 756 856 956 1056 C 19 H 29 648 748 848 948 C 21 H 1 684 784 884 984 C 21 H31 674 774 874 974 R and n are as previously defined. * In addition these saturated esters, derived from saturated acid compounds, are presented.

T he emp lo To a 250 ml 4-necked round bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet is charged with 30.83 g of ethyl sorbate, 99% and 94.82 g of Fluorotelome intermediate ZONYL BA. The mixture is heated to and maintained at approximately 125 ° C for approximately 2 hours, at which time 5 drops of titanate of TAP TYZOR are added and the temperature is increased to and maintained at approximately 150 ° C for approximately 268 hours, with additions of 5 additional drops of TPT TYZOR after 22 and 73 elapsed hours to produce the fluorinated ester. The mixing product contains 0.58% residual ZONYL BA by GC analysis and 53.3% fluoro by combustion analysis.

E j a lo 13 To a 250 ml 4-necked round bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet 1 of nitrogen is charged with 28.00 g of 2,4-hexadienoic acid (sorbic acid), 94.81 g of the Fluorotelomer ZONYL BA termediary and 0.31 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at approximately 130 ° C for approximately 269 hours to produce the fluorinated ester, at which time the mixture contains 0.27% residual ZONYL BA by GC analysis and 51.0% fluoro by combustion analysis.

E j a lo 14 To a 250 ml 4-necked round bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet 1 of nitrogen is charged with 31.23 g of trans-cinnamic acid, 96.25 g of the Fluorotelomer intermediate ZONYL BA and 0.21 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C for about 156 hours to produce the fluorinated ester, at which time the mixture contains 0.24% residual ZONYL BA by GC analysis and 51.5% fluoro by combustion analysis. The ester products having the following molecular weights are identified by the GC / MS analysis as compounds of the reaction mixture.

C9 9Hn 9 494 594 694 794 894 994 1094 1194 R and n are as previously defined E j p lo 15 To a 250 ml 4-necked round bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet 1 of nitrogen is charged with 48.95 g of dime ti 1 ita cona to, 97%, and 129.82 g of Fluorotelomer intermediate ZONYL BA. The mixture is heated to and maintained at about 139 ° C for about 66 hours, with the addition of 1.1955, 1.2020 and 0.5595 g 'of tetrais op r op i 1 titanate or TPT TYZOR at about zero, 18 and 44.5 hours elapsed, respectively. The reaction product mixture contains approximately 2.42% of residual ZONYL BA by GC analysis and 50.8% of fluoro by combustion analysis and the ester products having the following molecular weights are identified by GC / MS analysis. n 3 4 5 6 CH3 490 590 690 790 890 990 1090 C3H7 518 618 718 818 n 4 5 6 822 922 1022 1122 1022 1122 1222 n is as previously described. R is an alkyl radical introduced from the catalyst or the initiating ester.

* It exists when the acid groups react with the different homologs of the ZONYL BA.

E n g it 16 To a 250 ml 4-necked round bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet 1 of nitrogen is charged with 19.54 g of itaconic acid, 99%, 144.20 g of the Fluorotelomer intermediate ZONYL BA and 0.22 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C for about 134 hours to produce the fluorinated ester, at which time the mixture contains 2.19% of the residual ZONYL BA by GC analysis and 62.95% of fluoro by the analysis of c ombu sti. on E j p lo 17 To a 250 ml 4-necked round-bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet 1 is loaded with 28.3 g of 2-oct anhydride in addition to its protein, 84.2 g of Fluorotelomer intermediate ZONYL BA, 0.2 g of 70% aqueous phosphorous acid and 0.08 g of boric acid. The mixture is heated to and maintained at approximately 145 ° C for approximately 48 hours. The reaction mixture, isolated as a tannin, waxy solid, m.p. 42.4 ° C by differential scanning calorimetry (CED), contains 49.2% fluoro by combustion analysis and the ester products having the following molecular weights are identified by the GC / MS analysis. 4 5 6 7 3 1160 1260 1360 1460 4 1260 1360 1460 1560 1660 5 1260 1360 1460 1560 1660 6 1460 1560 1660 7 1560 1660 It is as previously defined E j emp lo 1 To a 250 ml 4-necked round-bottomed flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen dioxide filter is charged with 45.22 g of Flaxseed Fatty Acid Emery 644, 78.16 g of the glycols of bis- (perf 1 or roa 1 qu i 1 eti lme rc ap o) ne op enti 1 of the formula [F (CF2CF2) nCH2CH2SCH2] 2C (CH2OH ) 2, where n is 3 to 8, predominantly 3, 4 and 5, and 0.18 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C for about 42 hours to produce the fluorinated ester, at which time the mixture contains 0.48% residual ZONYL BA by GC analysis and 38.4% fluoro by combustion analysis. n.

Example 19 To a 250 ml 4-necked round bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet 1 of nitrogen is charged with 69.56 g of Fatty Acid of Flax Emery 644, 111.43 g of FX-42 and 0.15 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at approximately 145 ° C for approximately 72.5 hours to produce the fluorinated ester, at which time the mixture contains 0.41% residual FX-42 by GC analysis and 36.8% fluoro by combustion analysis. sti n.

E j p lo 20 To a 250 ml 4-necked round-bottomed flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen triazine is charged. with 26.63 g of 2-do of cen-1-i 1 succinic anhydride, 116.83 g of FX-42 and 0.18 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C for about 48 hours to produce the fluorinated ester, at which time the mixture is released from the functionality of the carboxylic acid / anhydride by the infrared analysis and It contains 44.9% fluoro by combustion analysis.

E j a lo 21 The synthesis of R-CO-S-X-Rf, where R is a hydrocarbon radical of the fatty acid, X is -CH2CH2-, and Rf is a radical of f 1 u or r o c a r b u r o of the formula F (CF2CF2) n-, where n is 4 to 7.

To a 250 ml 4-necked round bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a water condenser, and a nitrogen inlet 1 load with 75.02 gm of thiols of pe rf luo r oa l i i eti 1 o of the formula F (C F2 C F2) n CH2 CH2 SH, where n is 4 to 7, 48.76 gm of flax fatty acid Emery 644 and 0.16 gm of 70% aqueous phosphorous acid. The mixture is heated to and maintained at approximately 145 ° C for approximately 263 hours, at which time it contains approximately 0.13% of the residual fluorothiol by GC analysis, 36.1% of fluoro by the combustion analysis and the ester products having the following Molecular weights are identified by the GC / MS analysis. n 31 718 828 918 1018 C 17 H 35 746 846 946 1046 C 17 H 33 744 844 944 1044 C 17 H 32 742 842 942 C 17 H 29 740 840 940 R and n are as previously defined. * In addition these saturated thiol esters are presented, derived from said saturated acid compounds.

Comparative Example A To a 250 ml 4-necked round bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet is charged with 56.86 g of stearic acid, 90%, 75.98 g of Fluorotelomer intermediate ZONYL BA, and 0.20 g of 70% aqueous phosphorous acid. The mixture is heated to and maintained at approximately 145 ° C for approximately 24 hours to produce the fluorinated ester, at which time the mixture contains approximately 0.05% of residual ZONYL BA by GC analysis and 37.6% of fluoro by analysis of C ombu sti n.

Comparative Example B To a 250 ml 4-necked round bottom flask, adapted with a mechanical stirrer, a temperature control device, a Dean-Stark trap, a condenser, and a nitrogen inlet is charged with 25.96 g of di eti lma 1 eato, 97%, 137.02 g of Fluorotelomer intermediate ZONYL BA and 0.22 g of aqueous phosphorous acid. The mixture is heated to and maintained at about 145 ° C, with the addition of 1.4 g and 0.9 g of titrant titanate op opi 1 or TPT TIZOR and 2.0 g of diethyl 1 eato, 97%, after about 25 , 44.5 and 51 hours elapsed, respectively, for approximately 70 hours to produce the fluorinated ester, at which time the mixture contains 6.74% of residual ZONYL BA by GC analysis and 60.3% of fluoro by combustion analysis. The esters of maleic and fumaric acid having the following molecular weights are identified by the GC / MS analysis as compounds of the product mixture. 3 4 5 6 C, H. 490 590 690 790 C3H- 504 604 704 804 n 3 4 5 6 808 908 100 110 908 1008 110 120 1008 1108 120 130 n is as previously defined. R is an alkyl radical introduced from the catalyst or the initiating ester.

Example 22 The esters of Examples 1 through 21 and Comparative Examples A and B were mixed into the coating compositions as indicated in Tables 3-8 in an amount to give a fluoro concentration of 1000 μg / g in the mixed product and the resulting ester-containing coating composition is placed in a wash test panel, matt black P-121-10N Leneta. The coating is evaluated after desiccation by Test Method 1 to measure the angles of increased contact (Aum.) And decreased (Dis.), Tested for durability to washing by Test Method 2, and for the properties anti-blocking by Test Method 3 as described above.

TABLE 3 White Alkyd High Alkyl Enamel Paint Test Results Method 1 Method 2 Test Test Method 3 Test Coating Durability Antiblocking Dry To Wash Water Hexadecane Hexadecane Day of Cure Not from Aum. Dis. Aum. Dis Aum Dis. 1 H ± Control 83 42 18 0 15 0 1 124 87 81 63 70 38 2 124 99 81 65 70 40 3 127 89 82 59 72 52 8 9 10 4 125 85 82 51 70 42 5 123 88 81 69 70 40 9 10 6 124 96 82 75 71 49 7 124 86 83 39 74 46 9 10 8 124 81 83 47 66 37 9 124 91 81 72 74 55 8 10 10 127 92 82 34 71 29 11 126 89 81 19 69 16 12 125 94 82 78 74 49 13 15 90 82 78 74 49 8 9 10 14 124 85 81 49 72 48 9 10 15 125 84 84 66 80 60 9 9 10 16 122 83 83 68 81 57 17 118 81 81 34 61 37 18 124 86 81 78 75 54 19 115 62 79 69 53 20 20 118 99 79 73 67 36 8 9 21 124 85 80 68 66 39 Comparative Examples 130 82 43 16 B 108 79 82 57 52 TABLE 4 Test Results on Polyurethane with Film Brightness Test Method 1 Contact Angles A ua He xa de c an o Example No. Aum. Dis. Aum. Dis. Co trol 9 56 11 0 4 123 94 8 61 TABLE 5 Test Results on House Paint with Alloys for Outdoor Duron Test Method 1 Contact Angles A 7 ua He x a no no. From E j emp 1 or Aum. Dis. Aum. Dis. Control 98 53 12 8 1 125 84 82 39 TABLE 6 Test Results on Oil-Based Base Paint with Exterior Gloss SWP Test Method 1 Contact Angles Hexadecane Water Example No. Aum Dis. Aum. Dis Control 83 28 37 0 i 124 91 82 49 TABLE 7 Test Results on the Neutral Gel Layer Test Method 1 Contact Angles A g ua Hexade c ano No. From E em • P 1 or Aum. Dis. Aum. Dis. Control 61 25 0 0 14 66 28 75 42 16 90 47 83 64 Comparative Example R 72 32 72 TABLE 8 Test Results on the Neste WG3000 Gel Layer Test Method 1 Contact Angles A u a Hex ad e c an o No. From E j em P 1 or Aum. D i s. Aum. Dis. Control 73 49 0 0 1 95 51 69 24 18 112 48 76 54 It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (9)

1. A coating composition characterized in that it comprises: A. An ester of an unsaturated acid and a fluorinated alcohol or thiol selected from the group consisting of the formula la, Ib and 2, Rf-X-A-OC-R, Formula R, X-A-OC-R-Rx-CO-A-X-R f I Formula r Ib Formula 2 where: Rf is a C2-C20 perfluoroalkyl radical, or a C5-C38 perfluoroalkyl radical having at least one ether oxygen atom; R is a C3-C2 unsaturated aliphatic hydrocarbon radical a C8-C13 aryl radical having at least one non-aromatic double bond, or mixtures thereof; X is independently CH 2 I -CON (Ri) R S02N (R?) R2- or - (OCH2CHR3) 0-, wherein m is 1 to about 20; b is 3 to about 15; Ri is H or alkyl radical of 1 to about 4 carbon atoms, R 2 is C 1 -C 12 alkylene, and R 3 is H or C H 2 C 1; A e s O Rx is a divalent C3-C22 unsaturated aliphatic hydrocarbon radical; a divalent Ca-Ci3 aryl radical having at least one non-aromatic double bond, or mixtures thereof; e y y B. an alkyd, Type I urethane or unsaturated polyester resin; wherein a cured coating resulting from said coating composition has a contact angle for the hexadecane increased by at least about 40 degrees.

2. The composition according to claim 1, characterized in that R. s e selects from the group consisting of F (C F2) n- where e s up to about 20; b) CF3-CF-O- (CF2) ß- wherein e is 1 to CF3 about 5; Y c) where g is 1 to about 6, and h is about 3 to about 10.

3. The composition according to claim 1, characterized in that Rf is F (CF2) n, wherein n is 2 to about 20.

4. The composition according to claim 3, characterized in that R is a C 5 to C 8 unsaturated alkenyl group having at least one double bond.

5. The composition according to claim 1, characterized in that it has a contact angle for the hexadecane increased by at least 60 degrees.

6. The composition according to claim 1, characterized in that it has from about 50 to about 10,000 μg / g by weight of fluoro based on the non-volatile content of the coating composition.

7. A cured coating composition, characterized in that it comprises: A. an ester of an unsaturated acid and a fluorinated alcohol or thiol selected from the group consisting of the formula la, Ib, and 2 Rf-X-A-OC-R Formula Rf-X-A-OC-R-Rx-CO-A-X-Rf, F rmul a Ib Formula 2 where Rf is a C2-C2o perfluoroalkyl radical or a C5-C38 perfluoroalkyl radical having at least one ether oxygen atom; R is a C3-C2i unsaturated aliphatic hydrocarbon radical, a C8-Cn aryl radical having at least one non-aromatic double bond, or mixtures thereof; X is independently - (CH2) m-, -CON (Ri) R2-, S02N (R?) R2- or - (OCH2CHR3) bO-, wherein m is 1 to about 20; b is 3 to about 15; Ri is H or alkyl radical of 1 to about 4 carbon atoms, R 2 is alkylene i-C 12, and R 3 is H or C H 2 C 1; A e s O or S; Rx is a divalent C3-C22 unsaturated aliphatic hydrocarbon radical; a divalent C 8 -C 13 aryl radical which has at least one non-aromatic double bond, or mixtures thereof; a is 1 or 2; Y B. an alkyd, Type I urethane or unsaturated polyester resin; wherein a cured coating resulting from said coating composition has a contact angle for the hexadecane increased by at least about 40 degrees.

8. A method of improving the oil repellency of a composition for alkyd, Type I urethane or unsaturated polyester coating, characterized in that it comprises adding to said coating composition an effective amount of an unsaturated acid ester and an alcohol or fluorinated thiol selected from the group consisting of the formula la, Ib, and 2 Rf-X-A-OC-R, Formula Rf-X-A-0C-R-Rx-C0-A-X-R f / Fó rmu the Ib Formula 2 where: Rf is a C2-C2o perfluoroalkyl radical or a C-C38 perfluoroalkyl radical having at least one ether oxygen atom; R is a C3-C2i unsaturated aliphatic hydrocarbon radical, a C8-Ci3 aryl radical having at least one non-aromatic double bond, or mixtures thereof; X is independently - (CH2) m-, -CON (R?) R2-, S02N (R?) R2- or - (OCH2CHR3) b0-, wherein m is 1 to about 20; b is 3 to about 15; Ri is H or alkyl radical of 1 to about 4 carbon atoms, R 2 is C 1 -C 12 alkylene, and R 3 is H or C H 2 C 1; is Rx is a divalent C3-C22 unsaturated aliphatic hydrocarbon radical; a divalent C8-Cx3 aryl radical having at least one non-aromatic double bond, or mixtures thereof; and a is 1 or 2;

9. An ester of perfluoroalkyl alkenoate having the structure: Rf-X-0-CO-R characterized because O-CO-R is a residue of the C10-C 24 alkeneic acid containing at least 2 double bonds; X is a divalent radical containing 1-20 atoms in the chain; Y Rf is a perfluoroalkyl group Ci-20 selected from the group consisting of Rf-S02N (Et) -CH2CH2-R £ -S02N (Me) -CH2CH2 'Rf -S02N (Bu) -CH2CH2'