MXPA06007540A - Water-and oil-repellent fluoroacrylates - Google Patents

Abstract

(a) at least one fluorochemicalalcohol represented by the formula:wherein:n=1 to 4, R=hydrogen or an alkyl group of 1 to 4 carbon atoms, m=2 to 8, Rf=CnF2n+1, y=0 to 6, and q=1 to 8;(b) at least one unbranched symmetric diisocyanate;and (c) at least one hydroxy-terminated alkyl (meth) acrylate or 2-fluoro acrylate monomer having 2 to about 30 carbon atoms in its alkylene portion.

Description

Fortwo-letter codes and olker abbrevk? Ti < ms, r r to the "Guid-anne. Notes on Codes and Abbreviations" appearing atthcbtgin-ning ofeach regular Usue of &e PCT Gazette.

FLUOROACRILATOS REPELENTS TO WATER AND OIL Field of the Invention This invention relates to water and oil repellent fluoroacrylate monomers and polymers. BACKGROUND OF THE INVENTION Different fluorinated acrylic resins containing urethane linkages are known to have water and oil repellent properties (see, for example, US Patent No. 4,321,404 (Williams et al.), 4,778,915 (Lina et al.). , 4,920,190 (Lina et al.), 5,144,056 (Anton et al.), And 5,446,118 (Shen et al.). These resins can be polymerized and applied as coatings to substrates such as, for example, textiles, carpets, wall coverings, skin, and the like to impart water and oil repellency. Typically, these resins comprise long chain pendant perfluorinated groups. { for example, 8 carbon atoms or greater) because the long chains are easily aligned parallel to the adjacent hanging groups attached to the acrylic main chain units, and thus maximize the repellency to water and oil. However, groups containing long chain perfluorinated groups such as, for example, compounds containing perfluorooctyl can bioaccumulate in living organisms (see, for example, US Patent No. 5, -688,8-84). (Baker et al.)). Ref.:174108 Brief Description of the Invention In view of the foregoing, we recognize that there is a need for water and oil repellent acrylic resins that is less bioaccumulative. Briefly, in one aspect, the present invention provides water and oil repellent f luoroacrylates having short chain perfluorinated groups (5 carbon atoms or less), which are believed to be less toxic and less bioacu ulative than the longer chain perfluorinated groups (see, for example, WO 01/30873). The f luoroacrylates of the invention comprise the reaction product of: (a) at least one fluorochemical alcohol represented by the formula: CnF2n +? - X-OH where n = 1 to 5, ? fla,? f "CJHÜ.

R = hydrogen or alkyl group of 1 to 4 carbon atoms, m = 2 to 8, Rf = CnFn + ?, y = 0 to 6, and q = 1 to 8; (b) at least one unbranched symmetric diisocyanate; and (c) at least one monomer of 2-fluoroacrylate or hydroxy-terminated alkyl (meth) acrylate having 2 to about 30 carbon atoms in its alkylene portion. As used herein, the term "(meth) acrylate monomer" refers to both the acrylate monomers and the methacrylate monomers. The invention also provides fluoroacrylates represented by the following general formula: CnF2"+? - X-OC (O) NH-A-HNC (O) O- (CpH2p) (O) COC (R ') = CH2 where n = 1 to 5 -SOr- T33 C & 2 »-CO» - -CAm- R = hydrogen or alkyl group of 1 to 4 carbon atoms, m = 2 to 8, Rf = CnF2n + ?, y = 0 to 6, q = 1 to 8, A = a non-branched symmetric alkylene group, arylene group, or aralkylene group, P = 2 to 30, and R '= H, CH3, or F. It has been found that the fluoroacrylates of the invention exhibit good water and oil repellency properties. In view of the prior art, one would expect that fluoroacrylates derived from shorter perfluorinated chains would not be as effective in imparting water and oil repellency as those derived from longer perfluorinated chains (see, for example, US Patent No. 2,803,615). (Ahlbrecht et al.) And 3,787,351 (Olson)). Surprisingly, however, the fluoroacrylates of the invention exhibit comparable water and oil repellency with the fluoroacrylates with longer perfluorinated chains. The fluoroacrylates of the invention therefore meet the need in the art for water-repellent acrylic resins and polymerizable oils that are less bioaccumulative. In another aspect, the invention provides fluorinated isocyanates that are useful for making the fluoroacrylates of the invention. The fluorinated isocyanates can be represented by the following formula: C "F2n + 1-X-OC (O) NH-A-NCO where: n = 1 to 5 R = hydrogen or alkyl group of 1 to 4 carbon atoms, = 2 to 8, Rf = CnF2r? + ?, y = 0 to 6, q = 1 to 8, A = a non-branched symmetrical alkylene group, arylene group, or aralkylene group. In other aspects, this invention also provides fluorinated acrylic polymers comprising repeat units of the fluoroacrylates of the invention, coating compositions and release coating compositions comprising fluorinated acrylic polymers, and coated articles with coating compositions of the invention. removable coating.

Detailed Description of the Invention Fluorochemical alcohols which are useful in the fluoroacrylates of the invention can be represented by the formula: CnF2n +? - X-OH where: n = 1 to 5 - sog- Taí? Ft. - R £ C CyE.

R = hydrogen or alkyl group of 1 to 4 carbon atoms, m = 2 to 8, Rf = C__F2n + ?, y = 0 to 6, and q = 1 to 8.

Examples of suitable alcohol alcohols include CF3CH2OH, (CF3) 2CHOH, (CF3) 2CFCH2OH, C2F5S02NH (CH2) 20H, C2F5S02NCH3 (CH2) 20H, C2F5S02NCH3 (CH2) 40H, C2F5S03NC2H5 (CH2) 60H, C2F5 (CH2) 4OH, C2F5CON (CH2) 4OH, C3F7S02NCH3 (CH2) 30H, C3F7S02NH (CH2) 2 OH, C3F7CH2OH, C3F7CONH (CH2) 80H, C4F9 (CH2) 20H, C4F9S02NCH3 (CH2) 20H, C4F9CONH (CH2) 20H, C4F9SO2NCH3. { CH2) 40H, C4F9S02NH (CH2) 7OH, C4F9S02NC3H7 (CH2) 20H, C4F9S02NC4H9 (CH2) 20H, C5F ??? S02NCH3 (CH2) 2OH, C5F11CONH (CH2) 20H, and CsF (CH2) 40H. Preferably, n is 1 to 4; more preferably, n is 4. Preferably m is from 2 to 4. Preferably q is 2. pn. VT_. ni »1 * D Preferably, X is a" * "More preferably, X is "More preferably, X is selected from the group consisting of - "30-1 r9 (CH -.), - Preferred fluorochemical alcohols include, for example, C4F9S02NCH3 (CH2) 2OH, C4F9SO2NCH3 (CH2) OH, and C4F9 (CH2) 2OH. A preferred fluorochemical alcohol is C4F9SO2NCH3 (CH) 20H. Symmetric diisocyanates are diisocyanates that meet the three elements of symmetry as defined in Hawley's Condensed Chemical Dictionary 1067 (1997). First, they have a center of symmetry, around which the constituent atoms are placed in an orderly arrangement. There is only one center in the molecule, which may not be an atom. Second, they have a plane of symmetry, which divides the molecule into segments with an image in the mirror. Third, they have axes of symmetry, which can be represented by lines that pass through the center of symmetry. If the molecule is rotated, it will have the same position in space more than once with a full 360 ° rotation. As used herein, the term "unbranched" means that the symmetrical diisocyanate contains no subordinate chain of one or more carbon atoms. Representative examples of symmetric unbranched diisocyanates include, 4,4'-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), 1,4-phenylene diisocyanate (PDI), 1,4-butane diisocyanate (BDI), 1,8-octane diisocyanate (ODI), 1,12-dodecane diisocyanate, and 1,4-xylylene diisocyanate (XDI). Preferred non-branched symmetric diisocyanates include, for example, MDI, HDI, and PDI. A more preferred unbranched diisocyanate is MDI. In its pure form, MDI is commercially available Isonate ™ 125M from Ttow Chemical Ccmpany. { Midland, MI), and as Mondur ™ by Bayer Polymers (Pittsburgh, PA). The hydroxy-terminated 2-fluoroacrylate and (meth) acrylate alkyl monomers which are useful in the fluoroacrylates of the invention may have from 2 to about 30 carbon atoms (preferably, from 2 to about 12 carbon atoms) in their alkylene portion. Preferably, the monomer of alkyl (meth) acrylate terminated with hydroxy is an alkyl acrylate terminated with hydroxy. Preferred hydroxy-terminated alkyl acrylates include, for example, hydroxyethyl acrylate, hydroxy butyl acrylate, hydroxy hexyl acrylate, hydroxy decyl acrylate, hydroxy dodecyl acrylate and mixtures thereof. The fluoroacrylates of the invention can be prepared, for example, by first combining the fluorochemical alcohol and the unbranched symmetrical diisocyanate in a solvent, and then adding the hydroxy-terminated alkyl (meth) acrylate. Useful solvents include esters (eg, ethyl acetate), ketones (eg methyl ethyl ketone), ethers (eg, methyl tert-butyl ether), and aromatic solvents (eg, toluene). Preferably, the reaction mixture is stirred. The reaction can generally be carried out at a temperature between room temperature and about 120 ° C (preferably between about 50 ° C and about 70 ° C). Typically the reaction is carried out in the presence of a catalyst. Useful catalysts include bases (e.g., tertiary amines, alkoxides, and carboxylates), metal salts and chelates, organometallic compounds, acids, and urethanes. Preferably, the catalyst is an organotin compound. { for example, dibutyltin dilaurate (DBTDL) or a tertiary amine (eg, diazobicyclo [2.2.2] octane (DABCO)), or a combination thereof. More preferably, the catalyst is DBTDL. When fluorochemical alcohols represented by the formula CnF2n + the? S02NCH3 (CH2) m OH, where n = 2-5, m = 2 to 4, are reacted with MDI, the process described in U.S. Patent Application can be used Series No. 10/751142, entitled "Process For Preparing Fluorochemical Monoisocyanates", filed on December 31, 2003. The fluoroacrylates of the invention can be represented by the following general formula: CnF2"+? - X-OC (O) NH-A-HNC (O) O- (CpH2p) (O) COC (R ') = CH2 where n = 1 to 5, * £ "C C lay R = H or alkyl group of 1 to 4 carbon atoms, m = -2 to 8, Rf = CnF2n + ?, y = 0 to 6, q = 1 to 8, A = a non-branched symmetric alkylene group, arylene group, or aralkylene group, P = 2 to 30, and R '= H, CH3 or F. Preferably, n is 1 to 4; more preferably, n is 4. Preferably, q is 2. Preferably, X is and m is from 2 to 4. Preferably, A is selected from the group consisting of preferably, A is preferably, from 2 to 12; more preferably, p is selected from the group consisting of 2, 4, 6, 10 and 12; more preferably, p is 2. Preferably, R 'is H. The fluoroacrylates of the invention can be polymerized to produce a fluorinated acrylic polymer. Fluorinated acrylic polymers comprising repeating units of fluoroacrylates of the invention exhibit water and oil repellency properties. The fluoroacrylates of the invention can also be polymerized with one or more non-functional comonomers and / or functional comonomers. Non-functional comonomers such as, for example, alkyl acrylates can improve durability and film-forming properties. Representative examples of useful non-functional comonomers include methyl (meth) acrylate, butyl acrylate, isobutyl (meth) acrylate, hexyl acrylate, dodecyl acrylate, octadecyl acrylate. The non-functional comonomers can typically be copolymerized with the fluoroacrylates of the invention with a molar ratio of about up to 1: 1. The comonomers may provide properties such as, for example, adhesion, hydrophilicity, reactivity, or low glass transition temperatures. Groups that are useful in the functional comonomers include, for example, hydroxy, carboxy, quaternary ammonium, acetate, pyrrolidine, propylene glycol, sulfonic acid, trialkoxysilane and silicone. These groups can generally be introduced to the polymer by at least about 20 weight percent (preferably, less than about 5 weight percent). Useful functional comonomers include, for example, acrylic acid, methacrylic acid, N-vinyl 2-pyrrolidone, and hydroxypropyl acrylate. The fluoroacrylates of the invention can also be polymerized with polydimethyl siloxanes methacrylate functional such as, for example, methacryloxy propyl polydimethyl silicone, to prepare grafted copolymers of siloxane / fluorinated acrylics. The fluorinated acrylic polymers of the invention can be used in coating compositions to impart water and oil repellency to a wide variety of substrates. The coating compositions comprise a fluorinated acrylic polymer of the invention and a solvent (eg, water and / or an organic solvent). When the solvent is water, the coating composition typically also comprises a surfactant. The fluorinated acrylic polymers of the invention can be dissolved, suspended, or dispersed in a wide variety of solvents to form coating compositions suitable for coating on a substrate. The coating compositions generally contain from about 0.1 to about 10 percent fluorinated acrylic polymer (generally about 1 to about 5 percent), based on the weight of the coating composition. The coating compositions can be applied to a wide variety of substrates such as, for example, fibrous substrates, and hard substrates. Fibrous substrates include, for example, woven, knitted and non-woven fabrics, textiles, carpets, leather and paper. Hard substrates include, for example, glass, ceramic, masonry, concrete, natural stone, hand-made stone, grout, metals, wood, plastics and painted surfaces. The coating compositions can be applied to a substrate (or articles comprising a substrate) by standard methods such as, for example, spraying, filling, dipping, roller coating, brushing, or unloading. Optionally, the composition can be dried to remove any remaining water or solvent. The polymers and copolymers of the invention can be used for release coatings. Comonomers which are useful in release coatings include, for example, octadecyl acrylate, N-vinyl 2-pyrrolidinone, methacryloxy propyl dimethyl siloxane, acrylic acid, methacrylic acid, acrylonitrile and methyl acrylate. The release coating compositions may or may not require a cure step after being coated on a substrate. Coating compositions useful for release coatings can be applied to surfaces that require release properties of the adhesives. Suitable substrates for release coatings include, for example, paper, metal foils, sheets, non-woven fabrics, and thermoplastic resin films such as polyesters, polyamides, polyolefins, polycarbonates, and polyvinyl chloride. The release coating compositions can be applied to suitable substrates by means of conventional coating techniques such as, for example, wire entangled bar, direct gravure, Offset gravure, reverse roll, air knife, and drag knife coating. The resulting release coating compositions can provide effective release for a wide variety of pressure sensitive adhesives such as, for example, natural rubber-based adhesives, silicone-based adhesives, acrylic adhesives, and other elastomeric adhesives that form synthetic film. .

EXAMPLES Objectives and advantages of this invention are illustrated by means of the following examples, but the particular materials and amounts thereof are cited in these examples, as well as other conditions and details, should not be construed to inappropriately limit this invention.

Preparation of HOHA (6-hydroxyhexyl acrylate) 118 g (1 mole, available from Sigma-Aldrich) 1,6-hexanediol, 36 g (0.5 mole, available from Sigma Aldrich) AA, 1.0 < j of the p-toluenesulfonic acid hydrate (available from Sigma Aldrich), 0.016 g phenothiazine, 0.055 g of hydroquinone monomethyl ether (available from Sigma Aldrich) and 300 ml of heptane were stirred under reflux in a 1 L round bottom flask. with three mouths equipped with a modified Dean-Stark trap. After 5 hours at reflux, 8.4 ml (0.47 ml) of water was collected. Once cold, two layers were formed. The top layer contained hexanediol diacrylate and heptane. The lower layer (141.2 g) was analyzed by means of gas liquid chromatography (GLC) after derivatization with TFAA (trifluoroacetic anhydride available from Aldrich) as 13.9% of unreacted diol, 11.0% of desired monoacrylate, and a trace of diacrylate. The lower layer dissolved in 100 ml of ethyl acetate and washed three times with 100 ml of water, was run out at 55.7 g, 15% diol, 84% monoacrylate (HOHA), and 1% diacrylate. To the HOHA mixture prepared above (19 g), 100 ml of ethyl acetate were added and this solution was washed three times with 150 ml of water. The last wash gave an emulsion, which was frozen and melted to give two phases. The organic phase produced HOHA (50.1 g of red liquid, 99% pure).

Preparation of HOHMA (HO (CH2) 6OC (O) C (CH3) = CH2) HOHMA was prepared essentially according to the procedure described for HOHA except that an equimolar amount of MAA was replaced by AA. Preparation of HODDA (12-hydroxydecyl acrylate) In a manner similar to the HOHA preparation, 203 g (1.0 mole) dodecan-1,12-diol, 36.0 g (0.50 mole), 1.0 g were refluxed for 3 hours. AA, 0.018 g phenothiazine, 0. 034 hydroquinone monomethyl ether, and 350 ml of heptane, and then allowed to cool and form a slurry. Filtration yielded 147.0 g of solid (96% diol by GLC analysis). The filter was separated as 120 g of an oil, 2% diol, 80% monoacrylate, and 18% diacrylate.

Flash chromatography of 29.5 g of hexene-ethyl acetate 85-15 (% vol.) On 257 g of 280-400 mesh silica gel (available from Sigma-Aldrich) produced Pure HODDA (17.1 g). Preparation of C4F9S02NH (CH3) C4F9S02NH (CH3) was prepared essentially following the procedure described in U.S. Pat. No. 6,664,354 (Savu et al.), Example 1, Part A. Preparation of MeFBSE: C4F9S02N (CH3) CHCH2OH MeFBSE was prepared essentially following the procedure described in U.S. Pat. No. 6,664,354 (Savu et al.), Example 2, Part A.

Preparation of MeFESE: C2F5S02N (CH3) CH2CH2OH MeFESE was prepared essentially following the procedure described in U.S. Pat. No. 6,664,354 (Savu et al.), Example 2, Part A with the exception that C2F5S02F (prepared essentially as described in U.S. Patent 5,723,630) was used as raw material. Preparation of MeFBSEA: C4F9S02N (CH3) CH2CH2OC (O) CH = CH2 MeFBSEA was prepared essentially following the procedure described in U.S. Pat. No. 6,664,354 (Savu et al.), Example 2, Part A & B. Preparation of MeFESEA: C2F5SQ2N (CH3) CH2CH2OC (O) CH = CH2 A round bottom flask was charged with 16.0 g (0.0623 mol) C2F5S02N (CH3) (CH2) 2OH, 33.8 g of ethyl acetate, and 10.47 g (0.0810 moles) of diisopropylethylamine was placed in an ice bath and cooled to 7 ° C. The reaction was set with a pressure equalizing with an addition funnel under nitrogen containing 7.33 g (0.0810 mol) of acryloyl chloride which was added to the reaction for 12 minutes. At 200 minutes, 16.9 g of ethyl acetate was added to the reaction, which was washed sequentially with 30 g of 2% aqueous hydrochloric acid and 5% aqueous sodium bicarbonate, dried over anhydrous magnesium sulfate, filtered and concentrated in a rotary evaporator at 55 ° C under pressure. of the vacuum cleaner to provide the crude product 11.93 g. A 7 cm diameter chromatography column was filled with 230 g of silica gel (# SX1043U-3, grade 62, 60-200 mesh, from EM Science, Darmstadt, Germany), slurry with 60:40 by volume heptane ethyl acetate and chromatography of 11.93 g of product was performed using the column to provide after concentration 7.06 g of the desired product. Preparation of C8F? 7S02NMeC2H4? C (0) CH = CH2 (MeFOSEA) MeFOSEA was prepared essentially as described in U.S. Pat. No. 6,664,354 (Savu et al.), Example IA and Example 2A and 2B with the exception that C8F? 7S02F (available from Sigma-Aldrich) was used instead of C4F9S02F. Preparation of C4F9 (CH2) 2OC (0) CH = CH2 Similarly to the preparation of C2F5S02N (CH3) (CH2) 2OC (0) CH = CH2, 11.02 g (0.0417 mol) C4F9 (CH2) 2OH available from TCI America , Portland OR) and 7.01 g (0.0542 moles) diisopropylethylamine in 22.4 g of diethyl ether were reacted with 4.91 g (0.0542 moles) acryloyl chloride for 2 hours, washed sequentially with 30 g of 2% aqueous hydrochloric acid and bicarbonate of aqueous sodium at 5%. dried over anhydrous magnesium sulfate, filtered and concentrated in a rotary evaporator in a bath at room temperature under vacuum pressure to provide a crude product. This was combined with a similar preparation of C4F9 (CH2) 3OC (0) CH = CH2 made using the same raw material ratios, initiated with 8.0 g of C4F9 (CH2) 3? H to provide approximately 25 g of the crude product. To these combined products was added 0.005 g of p-methoxy phenol and 0.0013 g of phenothiazine, and the raw material was distilled under vacuum pressure with a head temperature of 67 ° C to provide 8.88 g of the desired product. Preparation of EOSH: (CH3 (OCH2CH2) nOC (Q) CH2SH) A 500 ml three-necked round bottom flask was charged with 25.96 g of CH3 (OCH2CH2) n0H (MW = 550; 47.20 mmol); available by Sigma-Aldrich), 4.35 g HSCH2C02H (47.28 mmol, available from Sigma-Aldrich), 2 drops of CF3SO3H catalyst, and 120 ml of toluene. The mixture was refluxed under nitrogen at 115-120 ° C with a mechanical stirrer for 8 hours. The water was removed by azeotropic distillation. The analysis of Fourier Transform Infrared Spectroscopy (FTIR) indicated the formation of EOSH. The solvent was removed using a rotary evaporator (27.60 g). Preparation of C4F9SC) 2N (CH3) C2H4? C (0) NHC6H4CH2C6H4 C0 (MeFBSE-MDI) A three liter three-necked round bottom flask was coupled with a heater, nitrogen inlet, reflux condenser and thermocouple was charged with MeFBSE (357.0 g; 1 .O mol) and MEK (600 ml) and heated to reflux, while 30 ml of MEK The mixture was then cooled to 30 ° C and treated with MDI (750 g, 3.0 moles). After the temperature of the mixture was increased to about 40 ° C for 4 hours, it was filtered and added to toluene (4 1). The resulting off-white precipitate was collected by filtration and a fresh crystallization of toluene (white solid, 689.4 g, 57% yield). The structure was confirmed using liquid chromatography / mass spectroscopy (LC / MS) and LC / UV analysis. Preparation of C4F9S02N (CH3) C2H4OC (0) HC6H4CH2C6H NHC00CH2CH20C (O) CH = CH2 (MeFBSE-MDI-HEA) A one liter flask containing 500 ml of ethyl acetate was heated under reflux under N2, and 100 ml was distilled of ethyl acetate. The remaining solvent was cooled in dry air and treated with 151.9 g of MeFBSE-MDI, 29.1 g of 2-hydroxyethyl acrylate, 2 drops of DBTDL, and 7 mg of phenothiazine. After 5 hours at 50 ° C, infrared spectroscopy indicated complete conversion of the isocyanate. The cloudy solution was filtered through diatomaceous earth 40 g and rinsed with hot ethyl acetate to give 473. 5 g of a clear solution (29.6% solids, yield as MeFBSE-MDI-HEA, 77%). Preparation of C2F5SQ2N (CH3) CH2CH2OC (0) NHC6H4CH2C6H4 CO (MeFESE-MDI) To a flask containing 37. 5 g (0.15 mol) of MDI in 75 g of heptane which was filtered at 50 ° C through a frit with porosity C to which two drops of DBTDL were added at 50 ° C were added 25 .7 g (0.10 g. moles) C2F5S02N (CH3) CH2CH2OH dropwise over 58 minutes. The resulting solid was filtered at 3.5 hours, rinsed with 120 g of heptane, and dried under vacuum under nitrogen to provide 69. 43 g of a white powder that was 71% solids, the rest was heptane. (49 .29 g, yield, 97.2%). Preparation of C2F5S02N (CH3) CH2CH2OC (0) NHC6H4CH2C6H4NHCOOCH2CH2OC (O) CH = CH2 (MeFESE-MDI-HEA) A 250 ml round bottom flask equipped with overhead stirrer was charged with 40 g of MeFESE-MDI (71 % solids, 0.056 moles), 100 g of ethyl acetate, 2 drops of dibutyltin dilaurate and heated to 50 ° C in a heating bath under nitrogen. Then 6.50 g (0.56 moles) of hydroxyethyl acrylate were added in one portion, followed by 6.3 mg of p-methoxyphenol. The bath temperature was adjusted to 0 ° C and the reaction proceeded for 14 hours. The reaction was allowed to cool to room temperature for two days, and an absence of the isocyanate peak at 2281 cm -1 was noted by means of PTIR. Phenothiazine (2 mg) was added to the reaction mixture which was then concentrated in a 55 ° C bath under vacuum pressure to yield 35.3 g of a white solid. The product was dissolved in 10 g ethyl acetate, and chromatography was performed on a chromatography column with a diameter of 7 cm filled with 230 g of silica gel (# SX1043U-3, grade 62, 60-200 mesh, from EM Science , Darmstadt, Germany), slurry with 50:50 volume of heptane: ethyl acetate to produce 20. 13 g of the product. Preparation of C4F9 (CH2) 2OC (0) NHC6H4CH2C6H4NCO (C4F9 (CH2) 20H-MDI) C F9 (CH2) 2? H-MDI was prepared in a manner similar to the MeFESE-MDI preparation except that 17.7 g (.071 mole) of MDI in 30 g of heptane was reacted with 12.5 g (0.047 mole) of C4F9 (CH2) 2OH. Preparation of C4F9 (CH2) 20C (0) NHC6H4CH2C6H4NHCOOCH2CH2OC (O) CH = CH2 (C4F9 (CH2) 2OH-MDI-HEA) C4F9 (CH2) .OH-MDI-HEA was prepared in a manner similar to the preparation of MeFESE-MDI -HEA except that 12.0 g (0.023 mole) of C4F9 (CH2) 2 OH-MDI were reacted with 2.71 g (0.023 mole) of hydroxyethyl acrylate in 40 g of ethyl acetate with DBTDL, followed by preparation and chromatography to provide 5-hydroxyethyl acrylate. . 8 g of the product. Preparation of CF3CH2OC (0) NHC6H4CH2C6H4NCOOCH2CH2OC (O) CH = CH2 (CF3CH2OH-MDI-HEA) A mixture of 33. 0 g of CF3CH2OH (available from Aldrich), 125 g of MDI, 2 drops of DBTDL and 400 g of heptane were stirred at 50 ° C for 20 hours, filtered while still hot, and then the solids were collected and re-crystallized from toluene to give .100 g of the adduct of CF3CH2OH-MDI. A solution of 7. 0 g of the adduct, 2.32 g of HEA, 1 drop of DBTDL, and 30 ml of dry THF were heated under N2 for 20 hours at about 60 ° C. Acetone (40 ml) was added to the resulting white slurry, a small amount of insoluble material was filtered off and the solution was separated into 7.6 g of white solid. Flash chromatography with 80/20 hexane / ethyl acetate (v / v) on 200 g of silica gel (280-400 mesh, Aldrich) gave 4.1 g of pure monomer. Preparation of poly-MeFBSE-MDI-HEA A 125 ml bottle was charged with 6.0 g of MeFBSE-MDI-HEA, 70 g of "VAZO 67", and 24 g of ethyl acetate. After purifying with nitrogen for 35 seconds, the bottle was kept in a water bath with rotation at 60 ° C for 15 hours. The resulting slurry was treated with about 50 ml of methanol, filtered and the solid was dispersed in 43 g of ethyl acetate. Upon heating, the solid dissolved, and once cooled, the same solid precipitated. General Procedure for the Examples and Comparative Examples Listed in Table 1 &; 2 For each example and comparative example, a -bottle of 125 mi was loaded with 3 .0-6. 0 g of fluoroacrylate listed in the table (prepared essentially as described above for the MeFBSE-MDI-HEA), 15-40 mg of "VAZO 67", and sufficient ethyl acetate to produce a concentration of 25-30% by weight of the monomer. Appropriate amounts of the comonomers were added to arrive at the weight% listed in Table 2. After purging with nitrogen for 35-60 seconds, the bottle was kept in a rotating water bath at 60 ° C for 24-48 hours. The product then precipitated with cooling. In some cases the resulting polymer solution was poured into 300-400 ml of methanol. The precipitated polymer was subsequently dispersed in ethyl acetate to yield 20-30% by weight of the polymer solution. With heating, the solid dissolved and once cooled, usually precipitated some of the solid. The addition of small amounts of DMF gave the complete solution. Dynamic Contact Angle Measurement A test solution, emulsion, or suspension (typically at about 3% solids) was applied to a nylon 66 film (available from DuPont) by dipping the film strips. Prior to coating, the film was cleaned with methyl alcohol. Using a small holder to grip one end of the nylon film, the strip was immersed in the treatment solution, and then slowly and gently removed from the solution. The coated strip was allowed to dry with dry air in a protected site for a minimum of 30 minutes and then cured for 10 minutes at 150 ° C. The contact angles of. forward and backward in the coated film using a Dynamic Contact Angle Analyzer CAHN, Model DCA 322 (a Wilhelmy balance device equipped with a computer for data control and processing, commercially available from ATI, Madison, Wl). Water and hexadecane were used to test the liquids. The values for both water and hexadecane were reported. The larger values of the contact angles are indicative of better repellency. Table 1. Examples 1-16 and Comparative Examples Cl-Cll Table 2. Examples 17-37 and Comparative Example C12 fifty Example 38: Preparation of MeFBSE-MDI-HEA / ODA / AA; 70/26/4 A 125 ml bottle with magnetic stirrer was charged with 9.46 g 37% MeFBSE-MDI-HEA solution in ethyl acetate (3.50 g solids, 4.84 mmol), 1.30 g ODA (4.005 mmol), 0.2 g AA (2.78 mmol), 28.55 g of ethyl acetate and 0.050 g "VAZO 67". The solution was bubbled with nitrogen for two minutes. The sealed bottle was placed in a 70 ° C hot oil bath and stirred for 24 hours. Example 39: Preparation of MeFBSE-MDI-HEA / ODA / A-174 at a ratio of 70/26/4 A 125 ml bottle with magnetic stirrer was charged with 9.46 g 37% MeFBSE-MDI-HEA solution in acetate. ethyl (3.50 g solids, 4.84 mmol), 1.30 g ODA (4.005 mmol), 0.2 g A-174 (0.805 mmol), 26.84 g of ethyl acetate and 0.050 g "VAZO 67". The solution was bubbled with nitrogen for two minutes. The sealed bottle was placed in a 70 ° C hot oil bath and stirred for 24 hours. Table 3. Examples 38-39 Example.40: Preparation of MeFBSE-MDI-HEA / EOSH; 3.0 / 1.0 A 125 ml bottle with magnetic stirrer was charged with 5.00 g of MeFBSE-MDI-HEA (6,920 mmoles), 0.52 g EOSH (2,308 mmoles), 26.92 g of ethyl acetate and 0.064 g "VAZO 67". The solution was bubbled with nitrogen for two minutes. The sealed bottle was placed in a 70 ° C hot oil bath with magnetic stirring for 24 hours. The resulting solution showed precipitation at room temperature. The addition of 5.0 g of DMF gave a clear solution. Example 41: Preparation of MeFBSE-MDI-HEA / EOSH; 6.0 / 1.0: A 125 ml bottle with magnetic stirrer was charged with 5.01 g of MeFBSE-MDI-HEA (6,934 mmoles), 0.72 g EOSH (1,154 mmoles), 26.96 g of ethyl acetate and 0.055 g "VAZO 67". The solution was bubbled with nitrogen for two minutes. The sealed bottle was placed in a 70 ° C hot oil bath with magnetic stirring for 24 hours. The resulting solution showed precipitation at room temperature. The addition of 5.0 g of DMF gave a clear solution. Example 42: Preparation of MeFBSE-MDI-HEA / EOSH; 8.3 / 1: A 125 ml bottle with magnetic stirrer was charged with 5.01 g of MeFBSE-MDI-HEA (6.925 mmoles), 0.52 g EOSH (0.833 mmoles), 26.60 g of ethyl acetate and 0.054 g "VAZO 67". The solution was bubbled with nitrogen for two minutes. The sealed bottle was placed in a 70 ° C hot oil bath with magnetic stirring for 24 hours. The resulting solution showed precipitation at room temperature. The addition of 5.0 g of DMF gave a clear solution. Example 43: Preparation of H (MeFBSE-MDI-HEA) 4-SC? H25 A 125 ml bottle with magnetic stirrer was charged with 4.99 g of MeFBSE-MDI-HEA (6.9078 mmole), 0.35 g DDSH (1729 mmole), 11.94 g of ethyl acetate and 0.055 g "VAZO 67". The solution was bubbled with nitrogen for two minutes. The sealed bottle was placed in a 70 ° C hot oil bath polymerized with magnetic stirring for 24 hours. The resulting solution precipitated as a white solid. The addition of 5.0 g of DMF gave a clear solution. Example 44: Preparation of H (MeFBSE-MDI-HEA) 8-SC? 2H25 A 125 ml bottle with magnetic stirrer was charged with 5.02 g of MeFBSE-MDI-HEA (6,940 mmole), 0.17 g DDSH (0.840 mmole), 12.0 g of ethyl acetate and 0.050 g "VAZO 67". The solution was bubbled with nitrogen for two minutes. The sealed bottle was placed in a 7 ° C hot oil bath polymerized with magnetic stirring for 24 hours. The resulting solution precipitated as a white solid.

The addition of 5 g of DMF changed the clear solution (22.2% solids).

Table 4 Ex emplos 40-44 Example 45: Preparation of MeFBSE-MDI-HEA / methacryloxy-propyl polydimethyl silicone, 80/20 grafted copolymer A 125 ml bottle was charged with 2.0 g of MeFBSE-MDI-HEA, 0.5 g methacryloxy-propyl polydimethyl silicone (available from Shin Etsu Chanical Co., Tokyo), 14.4 g of ethyl acetate and 26 mg "VAZO 67". The resulting mixture was purged with nitrogen for two minutes, and the bottle was sealed and maintained in a rotating water bath at 70 ° C for 24 hours. To the resulting cloudy solution was added 5.0 g of DMF. Analysis by size exclusion chromatography (SEC) showed 90.4% conversion with Mi = 13, 200; Mw = 28, 800 and Mw / Lfa. = 2.2. Example 46: Preparation of MeFBSE-MDI-HEA / methacryloxy propyl polydimethyl silicone grafted copolymer, 60/40 A 125 ml bottle was charged with 1.51 g of MeFBSE-MDI-HEA, 1.01 g methacryloxy-propyl polydimethyl silicone (available from Shin Etsu Chemical Co., - Tokyo), 14.4 g of ethyl acetate and 22 mg "VAZO 67". The resulting mixture was purged with nitrogen for two minutes, and the bottle was sealed and maintained in a rotating water bath at 70 ° C for 24 hours. To the resulting cloudy solution was added 5.0 g of DMF. Analysis by size exclusion chromatography (SEC) showed 85.4% conversion with Mn = 14,400; Mw = 36,300 and Mw / Mn = 2.5. Table 5. Examples 45-46 Example 47: Peel Coatings The copolymer of Example 27 was diluted to 5% solids with toluene. The solution was then coated with a bar (Mayer) entangled with wire on a 0.0406 mm (1.6 mils) prilled polyester terephthalate film. The coated film was adhered to a fibreboard structure and dried for 15 minutes at 65 ° C. The test method used to evaluate the release coatings was a modification of the industrial standard adhesion release test to evaluate the. coated materials pressure sensitive adhesives. The standard test is described in detail in various publications of the American Society for Testing and Materials (ASTM), Philadelphia, PA, and the Pressure Sensitive Tape Counsel (PSTC), Glenvie, 111. The standard method is described in detail below. The reference source of the standard test method is ASTM D3330-78 PSTC-1 (11/75). Strips of 2.54 cm by 15-24 cm of Scotch® Performance Masking Tape 233+ (available from 3 * M Company, St. Paul, MN) were unraveled on the polyester film r-coated with a rubber roller of 2.24. kg. The laminated samples were then aged for 1 week at 22 ° C and 50% relative humidity or 16 hours at 65 ° C. Prior to the test, samples aged with heat were equilibrated at 22 ° C and 50% relative humidity for 24 hours. The detachment test was carried out when assembling the laminate of the coated film / adhesive tape on the platform, of a slip / detachment device Instrumentors, Inc. (model 3M90) with doubly coated tape. Then the force required to remove the adhesive tape at 180 degrees and 228.6 cm was measured. The new adhesions of the tape were also measured by adhering the newly released adhesive tape to a clean glass plate and measuring adhesion detachment in a normal manner using the same Instrumentors slip / detach test device above, releasing again to 228.6 c. / min and with an angle of detachment of 180 degrees. The results of these peel tests are shown in Table 6. Comparative Example 13 (C13): Peel-off coating comprising MeFOSEA / MMA / St / AA, 60/16/15/9 120 g of MeFOSEA (C8F? 7SO2N (CH3) CH2CH2OC (0) CH = CH2) to a 2 liter reaction flask equipped with heating mantle, a condenser, N2 inlet and a stirrer. The flask was heated at 70 ° C to molten MeFOSEA. Then a preliminary mixture of 32 g of methyl methacrylate, 30 g of styrene, 18 g of acrylic acid, 6.0 g of Rhodacal DS-10 surfactant, 5.71 g of Zonyl ™ FSP surfactant (Dupont) and 600 g of deionized water were charged to the flask. . The resulting milky solution was purged with N2 for 5 minutes with 1 liter per minute and heated to 50 ° C followed by the addition of the initiator, 0.3 g of K2S20s (potassium persulfate), dissolved in 10 g of water. The reaction mixture was heated at 50 ° C for 1 hour. The temperature was increased to 75 ° C and the reaction was carried out for an additional 5 hours. The resulting emulsion was cooled to room temperature. The% solids that were 26% was measured, resulting in a conversion of 99.5%. The release coatings were prepared and tested as described in Example 45. The results are shown in Table 6 below.

Table 6. Example 47 and Comparative Example C13 Example 48 The copolymer of Example 45 was coated and tested according to the methods described in Example 47 with the exception that SCOTCH MAGIC TAPE 810 (available from 3M Company) was used instead of SCOTCH PERFORMACE MASKING TAPE 233+. The results are shown in Table 7 below. Table 7 Example 49 The release liner of Example 47 was prepared and tested according to the methods described above using a polyurea pressure sensitive adhesive that was prepared and coated as described in U.S. Pat. 6,569,521 (see Example 31). The detachment strength of the release liner and the subsequent new adhesion to the glass were measured. Three aging conditions were evaluated: 7 days at 22 ° C (relative humidity 50%), 7 days at 50 ° C and 3 days at 70 ° C. The results are shown in Table 8 below. Table 8 Different modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and perspective of this invention. It will be understood that this invention is not intended to be unduly limited by the illustrative embodiments and examples set forth herein such that the examples and embodiments are solely represented as a means of exemplifying the scope of the invention which attempts to be limited only by the claims set forth herein. as follows. 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.

Claims (43)

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

1. Fluoroacrylate, characterized in that it comprises the reaction product of: (a) at least one fluorochemical alcohol represented by the formula: CnF2n +? - X-OH where n = 1 to 5, s CyHa? , o - c v-, R = hydrogen or alkyl group of 1 to 4 carbon atoms, m = 2 to -8, Rf = CnF2n +? , y = 0 to 6, and q = 1 to 8; (b) at least one unbranched symmetric diisocyanate; and (c) at least one monomer of 2-fluoroacrylate or hydroxy-terminated alkyl (meth) acrylate having 2 to about 30 carbon atoms in its alkylene portion.

2. Fluoroacrylate in accordance with the claim 1, characterized in that X is

3. Fluoroacrylate according to claim 2, characterized in that the R is a methyl group.

4. Fluoroacrylate according to claim 3, characterized in that the m is 2 to 4.

5. Fluoroacrylate according to claim 1, characterized in that the n is 1 to 4.

6. Fluoroacrylate according to claim 5, characterized in that n is 4.

7. Fluoroacrylate according to claim 6, characterized in that the fluorochemical alcohol is selected from the group consisting of C4F9S02NCH3. { CH2) 2OH, C F9S02NCH3 (CH2) 4OH and C4F9 (CH2) 2OH.

8. Fluoroa-crilate according to claim 7, characterized in that the fluorochemical alcohol is -C4F9S02NCH3 (CH2) 20H.

9. Fluoroacrylate according to claim 1, characterized in that the unbranched symmetrical diisocyanate is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-phenylene diisocyanate.

10. Fluoroacrylate according to claim 9, characterized in that the unbranched symmetrical diisocyanate is 4,4'-diphenylmethane diisocyanate.

11. Fluoroacrylate according to claim 1, characterized in that the monomer of 2-fluoroacrylate or hydroxy-terminated alkyl (meth) acrylate having 2 to about 12 carbon atoms in its alkylene portion.

12. Fluoroacrylate according to claim 1, characterized in that the monomer of 2-fluoroacrylate or hydroxy-terminated alkyl (meth) acrylate is an acrylate monomer terminated with hydroxy.

13. Fluoroacrylate according to claim 12, characterized in that the alkyl hydroxy-terminated acrylate monomer is selected from the group consisting of hydroxy ethyl acrylate, hydroxy butyl acrylate, hydroxy hexyl acrylate, hydroxy decyl acrylate, hydroxy dodecyl acrylate.

14. Fluoroacrylate, characterized in that it comprises the reaction product of: (a) C4F9S02NCH3 (CH2) 2OH, (b) 4,4'-difenylmethane diisocyanate, and (c) hydroxyethyl acrylate or hydroxybutyl acrylate.

15. Fluoroacrylate represented by the following formula: CnF2n +? - X-OC (0) NH-A-HNC (0) 0- (CpH2p) (O) COC (R ') = CH2 characterized because n = 1 to 5 "CyHjjy H« c & « R = hydrogen or alkyl group of 1 to 4 carbon atoms, m = 2 to 8, Rf = CnF2n + ?, y = 0 to 6, q = 1 to 8, A = a non-branched symmetric alkylene group, arylene group, or aralkylene group, P = 2 to 30, and R '= H, CH3, or F.

16. Fluoroacrylate in accordance with the claim 15, characterized in that n is 1 to 4.

17. Fluoroacrylate in accordance with the claim 16, characterized in that n is 4.

18. Fluoroacrylate in accordance with the claim -sc? -nr < and! _, - 15, characterized in that X is

19. Fluoroacrylate according to claim 18, characterized in that the R is a CH3 group.

20. Fluoroacrylate according to claim 19, characterized in that the m is 2 to 4.

21. Fluoroacrylate according to claim 15, characterized in that the A is selected from the group that consists of -o-

22. Fluoroacrylate in accordance with the claim 21, characterized in that the A is - ^

23. Fluoroacrylate according to claim 15, characterized in that the p is 2 to 12.

24. Fluoroacrylate in accordance with the claim 23, characterized in that the. p is selected from the group consisting of 2, 4, 6, 10 and 12.

25. Fluoroacrylate in accordance with the claim 24, characterized in that the p is 2.

26. Fluoroacrylate according to claim 15, characterized in that the R 'is H.

27. The fluorinated isocyanate represented by the following general formula: CnF2n +? - X-0C (O) NH- A-NCO characterized because n = 1 to 5 -sos-i? N cy? i, - -co- * -? A_í R = hydrogen or alkyl group of 1 to 4 carbon atoms, m = 2 to 8, y = 0 to 6, q = 1 to 8, and A = a non-branched symmetric alkylene group; arylene group, or aralkylene group.

28. Fluorinated acrylic polymer, characterized in that it comprises repeating units of the chloroacrylate according to claim 1.

29. Fluorinated acrylic polymer according to claim 28, characterized in that it also comprises repeating units derived from one or more non-functional comonomers.

30. Fluorinated acrylic polymer according to claim 28, characterized in that it also comprises repeating units derived from one or more functional comonomers.

31. Coating composition, characterized in that it comprises a solvent and the fluorinated acrylic polymer according to claim 28.

32. Fluorinated acrylic polymer, characterized in that it comprises repeated units of fluoroacrylate according to claim 15.

33. Fluorinated acrylic polymer in accordance with with claim 32, characterized in that it also comprises repeating units derived from one or more non-functional comonomers.

34. Fluorinated acrylic polymer according to claim 32, characterized in that it also comprises repeating units derived from one or more functional comonomers.

35. Coating composition, characterized in that it comprises a solvent and the fluorinated acrylic polymer according to claim 32.

36. Article, characterized in that it comprises a substrate having one or more surfaces coated with the coating composition according to claim 31

37. Article according to claim 36, characterized in that the substrate is a hard substrate or a fibrous substrate.

38. Article, characterized in that it comprises a substrate having one or more surfaces coated with the coating composition according to claim 35.

39. Article according to claim 38, characterized in that the substrate is a hard substrate or a fibrous substrate. .

40. Removable coating composition, characterized in that it comprises a solvent and the fluorinated acrylic polymer according to claim 28.

41. Removable coating composition, characterized in that it comprises a solvent and the fluorinated acrylic polymer according to claim 32.

42. Article, characterized in that it comprises a substrate having one or more surfaces coated with the release coating composition according to claim 40

43. Article, characterized in that it comprises a substrate having one or more surfaces coated with the release coating composition according to claim 41.