MXPA98005400A - Preparation of fluora polymers - Google Patents

Abstract

Disclosed is a method for preparing fluorinated emulsion polymers, which reduce or eliminate the need for fluorinated surfactants, this method comprises the steps of: a) supplying a reaction mixture, which includes water, a surfactant, a mixture of monomers having at least one fluorinated monomer, at least one non-fluorinated monomer, with high solubility in water, and, optionally, at least one non-fluorinated monomer having low water solubility, a macromolecular organic compound having a hydrophobic cavity; ) polymerize this monomer mixture

Description

PREPARATION OF FLUORITE POLYMERS The present invention relates to the preparation of fluorinated polymers. In particular, the present invention relates to an improved preparation of fluorinated polymers in emulsion. Fluorinated polymers have many convenient properties, such as superior weather resistance, high temperature resistance, water and oil repellency, low surface tension, chemical inertness and low flammability. These properties have resulted in the use of fluorinated polymers as coating materials for textiles and various substrates in many industrial areas. It is well known that it is very difficult to prepare emulsion polymers from perfluorinated monomers, particularly those containing long perfluorinated alkyl chains, such as fluoroalkyl groups with 4 to 20 carbon atoms, because these monomers are inherently insoluble in water and have poor solubility in most organic hydrocarbon solvents and monomers. The insolubility of the perfluorinated monomers limits their ability to be transported from the droplets of monomers to the polymerization particles. As a result, the particle size distribution is wide, the composition of a copolymer may not be uniform and high levels of gel are formed during polymerization. This gel formation is not convenient. Various methods of polymerizing fluorinated monomers are known, such as by using an organic solvent having high solubility in both water and perfluorinated monomers. Such solvents aid in the transport of monomers from the droplets of monomers to the polymerization particles. Other methods use relatively high levels of fluorinated surfactants to avoid gels or a combination of a fluorinated surfactant and a compatibilizer, which contains a perfluorinated segment and a hydrocarbon segment. All these methods have the disadvantage of introducing "foreign" components to the polymer latex. Solvents that contribute to the content of volatile organic compounds ("VOC") and perfluorinated surfactants dilute the polymer content and end up in the polymer film, where they can migrate and thus alter the surface composition and properties of the film. Likewise, the use of large amounts of fluorinated surfactants is added to the cost of polymer latex. However, reducing the amount of the fluorinated surfactants leads to an increase in gel formation, which is inconvenient.

The patent of E.U.A. No. 5,521,266 (Lau) discloses emulsion polymerization of hydrophobic hydrocarbon monomers with the use of cyclodextrin. The presence of the cyclodextrin facilitates the transport of the long alkyl chain hydrophobic monomers through the aqueous phase, so they can be homo- or copolymerized in a conventional emulsion polymerization process. The applicability of this method of emulsion polymerization to perfluorinated monomers is not disclosed. The incompatibility of fluorocarbons with hydrocarbons or water is well known, as is evident from the use of fluorocarbon coatings for non-tacky cooking surfaces. The cavity of the cyclodextrin is a sugar ring that has hydroxylated hydrocarbons. It is unexpected that cyclodextrins can be used to transport fluorinated monomers through the aqueous phase in emulsion polymerizations, and is not recognized in the patent of US Pat. No. 5,521,266. The present invention is directed to overcoming the problems associated with known methods of preparing the fluorinated emulsion polymers. The present invention provides a method for preparing a fluorinated emulsion polymer, comprising, as polymerized units, at least one fluorinated monomer and at least one non-fluorinated monomer, having high water solubility., which includes the steps of: a) supplying a reaction mixture, comprising: i) water, ii) a surfactant, iii) a monomer mixture comprising from 1 to 99 weight percent of at least one fluorinated monomer , from 1 to 10 weight percent of at least one non-fluorinated monomer, which has high solubility in water and from 0 to 98 weight percent of at least one non-fluorinated monomer, which has low water solubility, iv) a macromolecular organic compound, which has a hydrophobic cavity and b) polymerize the monomer mixture. The present invention further provides a composition comprising a macromolecular organic compound and a. fluorinated emulsion polymer, comprising, as polymerized units, from 1 to 99 weight percent of at least one fluorinated monomer, from 1 to 10 weight percent of at least one non-fluorinated monomer, which has a high solubility in water , and from 0 to 98 weight percent of at least one non-fluorinated monomer having a low solubility in water.

The present invention further provides an article comprising a coated substrate, wherein the coating includes the above composition. The present invention provides a method for preparing fluorinated emulsion polymers, which reduce or eliminate the need for a fluorinated surfactant. The present invention also provides a method for preparing fluorinated emulsion polymers, which have reduced gel formation. As used herein, the term "having low water solubility" means a solubility in water, at a temperature in the range of 25 to 50 ° C, not greater than 200 millimoles / liter. The term "having high solubility in water" means a solubility in water, at temperatures in the range of 25 to 50 ° C, greater than 200 millimoles / liter. As used herein, the term "(meth) acrylate" refers to both methacrylate and acrylic, the term "(meth) acrylic" refers to methacrylic and acrylic, and the term "(meth) acrylamide" refers to methacrylamide and acrylamide. The term "fluoroalkyl" means a partially fluorinated or perfluorinated (C 1 -C 20) alkyl. "Alkyl" means a linear or branched alkyl. All amounts are percentages by weight, unless otherwise indicated, and all ranges of percentages by weight are inclusive. As used herein, the following abbreviations apply: "g" = grams; "AATCC" = American Association of Textile Chemists and Colorists; "BA" = butyl acrylate; "MMA" = methyl methacrylate; "MAA" = methacrylic acid; 2-EHA "= 2-ethylhexyl acrylate; and" STY "= styrene Suitable fluorinated monomers include, but are not limited to: fluoroalkyl (meth) acrylate; fluoroalkylsulfoamidoethyl (meth) acrylate; fluoroalkylamidoethyl (meth) acrylate; fluoroalkyl (meth) acrylamide; fluoroalkylpropyl (meth) acrylate; fluoroalkylethyl poly (alkylene oxide) (meth) acrylate; fluoroalkylsulfoethyl (meth) acrylate; fluoroalkylethyl vinyl ether, - fluoro-alkylethyl-poly (ethylene oxide) -vinyl ether, pentafluorostyrene, fluoroalkyl styrene, fluorinated α-olefins, perfluorobutadiene, 1-fluoroalkylperfluorobutadiene, di (meth) acrylate of aH, aH, coH, βH-perfluoroalkanediol, and β-substituted fluoroalkyl (meth) acrylate. Preferred fluorinated monomers have a fluoroalkyl group with 4 to 20 carbon atoms Particularly preferred is fluoroalkyl (meth) acrylate (Cg-C2o) • Especially preferred fluorinated monomers are perfluorooctylethyl methacrylate and perfluorooctylethyl acrylate. Suitable non-fluorinated monomers, which have a water solubility, include, but are not limited to: α, β-ethylenically unsaturated monomers, such as primary alkenes and alkyl-substituted styrene; α-methyl styrene; vinyl toluene; vinyl esters of carboxylic acids (C4-C30), such as vinyl 2-ethylhexanoate and vinyl neodecanoate; vinyl chloride; vinylidene chloride; N-alkyl-substituted (meth) acrylamide, such as octyl acrylamide and maleic acid amide; vinyl-alkyl or aryl ethers with (C3-C30) alkyl groups, such as stearyl vinyl ether, alkyl (CT_-C3Q) esters of (meth) acrylic acid, such as methyl methacrylate, (met) ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, palm (methyl) methacrylate, (meth) ) stearyl acrylate; unsaturated vinyl esters of (meth) acrylic acid, such as those derived from fatty acids and fatty acids; multifunctional monomers, such as pentaerythritol triacrylate; and monomers derived from cholesterol. These monomers may also contain functionality, such as, but not limited to: hydroxy, amido, aldehyde, ureido and polyether. Suitable non-fluorinated monomers, which have high solubility in water, include, but are not limited to: monoethylenically unsaturated monomers, which contain acid functionality, such as monomers containing at least one carboxylic acid group, including acrylic acid, methacrylic acid, (meth) acryloxy-propionic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, monoalkyl maleates, monoalkyl fumarate and monoalkyl itaconates; (meth) acrylates substituted with acid, sulfoethyl methacrylate and (meth) phosphoethyl acrylate; (meth) acrylamides substituted with acid, such as 2-acrylamido-2-methylpropylsulfonic acid and the alkali metal and ammonium salts of such monomers acidic and acid-substituted functional groups; (meth) acrylates and basic substituted (meth) acrylamides, such as the amine-substituted methacrylates, including dimethylaminoethyl methacrylate, tertiary butyl methacrylate-aminoethyl and dimethylaminopropyl methacrylamide; acrylonitrile; ) substituted acrylamide and (meth) acrylamide, such as diacetone acrylamide, (meth) acrolein, and methyl acrylate Surfactants suitable for use in the method of the present invention include all anionic, cationic and nonionic surfactants , which can be used in emulsion polymerization Such surfactants include non-fluorinated surfactants and fluorine Mixtures of surfactants can be used, which include mixtures of non-fluorinated surfactants and fluorinated surfactants. Preferred surfactants are the non-fluorinated anionic surfactants, non-fluorinated nonionic surfactants, fluorinated anionic surfactants, fluorinated nonionic surfactants, and mixtures thereof. It is also preferred that at least one fluorinated surfactant be used in the method of the present invention. Particularly preferred are mixtures of non-fluorinated anionic surfactants with fluorinated surfactants. Suitable non-fluorinated nonionic surfactants include, but are not limited to: ethoxylated octylphenols; ethoxylated nonylphenols; and ethoxylated fatty alcohols: Suitable non-fluorinated anionic surfactants include, but are not limited to: sodium lauryl sulfate, sodium dodecylbenzene sulfonate; sulphated and ethoxylated derivatives of nonylphenols, octylphenols and fatty alcohols; and esterified sulfosuccinates. Preferred non-fluorinated anionic surfactants are sodium lauryl sulfate, salts of fatty acids and the salt of sulphonated nonylphenoxypoly (ethylene oxide) ethanol. Suitable non-fluorinated cationic surfactants include, but are not limited to: laurylpyridinium chlorides; cetyldimethyl amine acetate; and (C5-C18 alkyl) -dimethylbenzyl ammonium chlorides Suitable fluorinated agents include, but are not limited to: salts of fluoroalkyl (C5-C20) carboxylic acid; salts of fluoroalkyl (C4-C20) sulfonic acid; salts of fluoroalkyl (C4-C20) -benzenesulfonic acid, fluoroalkyl (C4-C20) -poly (ethylene oxide) ethanol, - salts of 3-fluoroalkyl (C] _ Cg) -ethoxypropionic acid, salts of 3-fluoroalkyl (C) ] _- Cg) ethylthio-propionic, salts of 3-fluoroalkyl (C] _-Cg) ethylamino-propionic acid, salts of fluoroalkyl (C4-C20) -trialkyl (C] _ Cg) -ammonium, salts of fluoroalkyl acid (C4-C20) -poly (fluoroalkyleneoxide) -sulfonic acid: salt of fluoroalkyl (C4-C20) -amido-alkylene-trialkyl (C? -G) -ammonium; salt of fluoroalkyl (C4-C20) sulfonamidoalkylene-trialkyl (C ] _- Cg) -ammonium and salts of 3-fluoroalkyl (C4-C20) -sulfoamidoethylaminopropionic acid The counterions of the fluorinated anionic surfactants can be cations of mono-, i- or tri-valent. Fluorinated, nonionic and anionic surfactants are preferred. More preferred fluorinated surfactants are perfluoroalkylethyl poly (ethylene oxide) ethanol and the lithium salt of 3- (perfluoroalkylethylthio) propionic acid. The total amount of the surfactant may be between 0.1 and 10 percent, and is preferably 0.5 to 5 percent by weight, based on the total weight of the monomer in the monomer emulsion. It is preferred that the total amount of the fluorinated surfactant be from 0.01 to 5 percent, preferably from 0.1 to 2 percent by weight, based on the total weight of monomers in the monomer emulsion. When the method of the present invention is used to prepare fluorinated emulsion polymers having a high percentage, such as 90 weight percent or more, of the fluorinated monomer, it is preferred that only the fluorinated surfactant be used. When the method of the present invention is used to prepare fluorinated emulsion polymers having less than 90 weight percent fluorinated monomers, it is preferred that the fluorinated surfactant be used in combination with the non-fluorinated surfactant. It is also preferred that the non-fluorinated surfactant be anionic. When both surfactants, fluorinated and non-fluorinated, are used, it is preferred that the weight ratio of the fluorinated surfactant to the non-fluorinated surfactant be in the range of 80:20 to 20:80. The macromolecular organic compounds having a hydrophobic cavity, useful in this invention, are known, and are described, for example, in the patent of US Pat. No. 5,521,266. Suitable macromolecular organic compounds include, but are not limited to: cyclodextrin and cyclodextrin derivatives; oligosaccharides having a hydrophobic cavity, such as cycloinulohexose, cycloinuloheptose and cycloinulooctose; calixarenos; and cavitandos. The cyclodextrin and cyclodextrin derivatives useful in the method of the invention are limited only by their solubility under particular polymerization conditions. Suitable cyclodextrins useful in this invention include, but are not limited to: a-cyclodextrin; β-cyclodextrin and β-cyclodextrin. Suitable derivatives of the cyclodextrin include, but are not limited to: the methyl, triacetyl, hydroxypropyl and hydroxyethyl derivatives of α-cyclodextrin; β-cyclodextrin and β-cyclodextrin. Preferred macromolecular organic compounds, which have a hydrophobic cavity, are cyclodextrin and cyclodextrin derivatives. The preferred derivative of the cyclodextrin is methyl β-cyclodextrin. The water, surfactant, monomer mixture and macromolecular compound can be added to the reaction vessel in any order. The macromolecular organic compound, which has a hydrophobic cavity, can be combined with the monomer mixture in any way. The macromolecular organic compound can be mixed with the fluorinated monomer and that mixture, together with the non-fluorinated monomer, having a high solubility in water, surfactant and any optional monomer, can be added to the reaction vessel. In the alternative, the macromolecular organic compound can be mixed with the monomer mixture before adding the mixture to the reaction vessel. In another alternative, the macromolecular organic compound can be added to the reaction vessel before, during or after the monomer mixture has been added to the reaction vessel. It is preferred to add the macromolecular organic compound to the reaction vessel before adding the monomer mixture. In general, the molar ratio of the macromolecular organic compound to the fluorinated monomer is in the range of 5: 1 to 1: 5000, preferably in the range of 1: 1 to 1: 1000, and more preferably between 1: 1 and 1: 500 . It is generally only necessary to have molar ratios in the catalytic range, such as from 1: 1 to 1: 500. The selection of the type and amounts of the crosslinking agents and the control of the pH, the rate of addition of the various components, the level of solids and the reaction temperature for the emulsion polymerization are well known to those skilled in the art. the emulsion polymerization. A free radical initiator was used in the emulsion polymerizations. Suitable free radial initiators include, but are not limited to: hydrogen peroxide; tertiary butyl hydroperoxide; Sodium, potassium, lithium and ammonium persulfate. A reducing agent, such as a bisulfite, including an alkali metal metabisulfite, hydrosulite and hyposulfite; and the sulfoxylate of a sodium formaldehyde or a reducing sugar, such as ascorbic acid, can be used in combination with the initiator to form a redox system. The amount of the initiator may generally be from 0.01 to 2 weight percent, based on the total weight of the monomer. When a redox system is used, the amount of the reducing agent is generally in the range of 0.01 to 2 weight percent, based on the total weight of the monomer. Transition metal catalysts, such as iron salts, can also be used. The range of the polymerization temperature generally varies from 10 to 100 ° C. This temperature range is preferably 75 to 90 ° C in the case of persulfate systems. In the case of redox systems, the temperature range is preferably 20 to 75 ° C. The compositions of the invention optionally contain fluorinated surfactants. When the fluorinated surfactant is present in the compositions, it is preferred that this fluorinated surfactant be nonionic or anionic. More preferred fluorinated surfactants are perfluoroalkylethyl-poly (ethylene oxide) -ethanol and the lithium salt of 3- (perfluoroalkyl-ethylthio) propionic acid. The compositions, prepared according to the method of the present invention, are useful in high performance coatings, such as coatings for fibers and textiles, slabs, bricks, cement, concrete and components in admixture in any formulation, instead of wax or silicones. The addition of fluorinated emulsion polymers to conventional formulations, instead of wax or silicones, provides water repellency to the surfaces coated with the formulations. Fluorinated polymers can also be used in delivering adhesive properties to highly hydrophobic surfaces, such as polytetrafluoroethylene. The fluorinated polymers can be applied to the highly hydrophobic surface as an adhesive, as a coating or in admixture with a coating to be applied.

EXAMPLES The level of the wet gel was determined by collecting the unfiltered material from sieves of 60 and 325 mesh, compressing the material to expel the excess water and weighing the compressed material on a scale. The following surfactants and monomers were used in the Examples.

Rhodapex® CO-436 Sodium salt of the sulfated polyethoxynonophenol, as a 59% aqueous solution.

SLS Sodium lauryl sulfate, used as a 28% aqueous solution Zonyl® TM perfluoroalkylethyl methacrylate CH2 = C (CH3) C02CH2CH2 (CF2) nCF3, n = 3-19 Zonyl® TAN Perfluoroalkylethyl acrylate, CH2 = CHC02CH2CH2 (CF2) nCF3, n = 5-17 Zonyl® FSN Perfluoroalkylethyl-poly (ethylene oxide) ethanol, a non-ionic fluorinated surfactant, as a 40% solution in a 50/50 mixture of water / isopropanol.

Zonyl® FSA Lithium salt of 3- (perfluoroalkylethylthio) -propionic acid, an anionic fluorinated surfactant, as a 25% solution in a 50/50 mixture of water / isopropanol CD methyl-b-cyclodextrin Zonyl® is a trademark of DuPont Company. Rhodapex® is a trademark of Rhone-Poulenc Chimie.

Example 1 Preparation of the monomer emulsion. A monomer mixture of 150 g of butyl acrylate, 340 g of methyl methacrylate, 500 g of Zonyl ™ and 10 g of methacrylic acid, and an aqueous mixture of 300 g of deionized water, 6.7 g of Rhodapex CO-436 and g of Zonyl FSN, were heated at 60 ° C in separate containers. Next, the two hot mixes were combined and homogenized to form a stable monomer emulsion. This stable emulsion was used hot or after cooling to room temperature.

Polymerization A 3 liter round bottom flask was equipped with a condenser, a mechanical stirrer, a thermal pair, a monomer charge line, an initiator charge line and a nitrogen inlet. To the flask were added 400 g of deionized water, 10 g of Rhodapex CO-436, a surfactant, and 15 g of Zonyl FSN, a surfactant. The contents of the flask were stirred and heated to 81 ° C under a nitrogen atmosphere. To the flask was added 10 g of a 50.3% aqueous solution of the CD, followed by 20 g of deionized water. To the flask were added 35.5 g of the monomer emulsion described above and a buffer solution of 3.5 g of sodium carbonate and 20 g of deionized water. After 2 minutes of stirring, an initiator solution of 2 g of ammonium persulfate and 20 g of deionized water was added to the flask. An exothermic reaction of about 2 ° C was usually observed after the addition of the initiator solution. Approximately 10 minutes after the temperature peak of the exothermic reaction, the remainder of the monomer emulsion and a second initiator solution of 1 g of ammonium persulfate and 50 g of deionized water were gradually added to the flask for a period of 60 minutes. , while the temperature was maintained at 81 ° C. The contents of the flask were maintained at 81 ° C for an additional 15 minutes, after completing the charges, and then cooled to 50 ° C. During cooling, 1 g of a 0.1% ferrous sulfate solution was added to the flask at 70 ° C. After 2 minutes, 0.3 g of a 70% t-butyl hydroperoxide solution, in admixture with 10 g of deionized water and 0.15 g of sodium sulfoxylate formaldehyde, dissolved in 10 g of deionized water, were added separately. At 50 ° C, another 0.3 g of the t-butyl hydroperoxide solution in admixture with 10 g of deionized water and another 0.15 g of sodium sulfoxylate formaldehyde, dissolved in 10 g of deionized water, were added separately to the flask. The final emulsion was then neutralized to a pH of 8-9 with the addition, in drops, of an ammonium hydroxide solution. The neutralized emulsion was then filtered through a 60 mesh screen and 325. The data for this polymer is found in the following Table 1.

Eg use 2 a. 6 The procedures described in the Example 1, except that the amount of the fluorinated surfactant and the CD were varied and a different hydrocarbon surfactant was used in Example 5, as indicated in Table 1. Comparative Examples Cl to C4 The procedures described in Example 1, except that the CD was not used and the amount of the fluorinated surfactant was varied, as indicated in Table 1.

TABLE 1 The above data shows that the use of a macromolecular organic compound, which has a hydrophobic cavity in the emulsion polymerization of the fluorinated monomers, greatly reduces or eliminates the need for fluorinated surfactants and reduces the amount of the gel formed during the polymerization.

Example 7 Monomer Emulsion An emulsion of monomers was prepared by homogenizing at 60 ° C an organic mixture comprising 280 g of 2-ethylhexyl acrylate, 410 g of styrene, 300 g of Zonyl ™ and 10 g of methacrylic acid, and at 60 ° C an aqueous mixture comprising 300 g of deionized water, 10 g of Rhodapex CO-436 and 15 g of a Zonyl FSN solution. The stable emulsion was used hot or after cooling to room temperature.

Polymerization. Using the same arrangement described in Example 1, 400 g of deionized water, 15 g of a Rhodapex CO-436 surfactant solution and 22.5 g of the Zonyl FSN surfactant were added to the flask. The contents of the flask were heated to 85 ° C, under a nitrogen atmosphere, followed by the addition of 20 g of an aqueous solution of the CD and 20 g of deionized water. To the flask were added 35.5 g of the monomer emulsion described above and a buffer solution of 3.5 g of sodium carbonate and 20 g of deionized water. After 2 minutes of stirring, an initiator solution of 2 g of ammonium persulfate and 20 g of deionized water was added to the flask. An exothermic reaction of about 2 ° C was usually observed after the addition of the initiator solution. Approximately 10 minutes after the temperature peak of the exothermic reaction, the remainder of the monomer emulsion and a second initiator solution of 1 g of ammonium persulfate and 50 g of deionized water were gradually added to the flask for a period of 60 minutes. , while the temperature was maintained at 81 ° C. The contents of the flask were maintained at 81 ° C for an additional 15 minutes, after completing the charges, and then cooled to 50 ° C. During cooling, 1 g of a 0.1% ferrous sulfate solution was added to the flask at 70 ° C. After 2 minutes, 0.3 g of a 70% t-butyl hydroperoxide solution, in admixture with 10 g of deionized water and 0.15 g of sodium sulfoxylate formaldehyde, dissolved in 10 g of deionized water, were added separately. At 50 ° C, another 0.3 g of the t-butyl hydroperoxide solution in admixture with 10 g of deionized water and another 0.15 g of sodium sulfoxylate formaldehyde, dissolved in 10 g of deionized water, were added separately to the flask. The final emulsion was then neutralized to a pH of 8-9 with the addition, in drops, of an ammonium hydroxide solution. The neutralized emulsion was then filtered through a 60 mesh and 325 mesh screen.

Example 8 The polymer was prepared using the procedures described in Example 7, except that the levels of the surfactant were reduced. The amounts of the surfactant used in the monomer emulsion were 9.33 g of Rhodapex CO-436 and 6 g of a Zonyl FSN solution. The amounts of the surfactant added to the flask were 14 g of the Rhodapex CO-436 solution and 9 g of the Zonyl FSN solution.

Example 9 The polymer was prepared using the procedures described in Example 8, except that the fluorinated surfactant used was the anionic surfactant Zonyl FSA.

Example 9A The polymer was prepared using the procedures described in Example 7, except that a fluorinated surfactant was not used.

Example 10 The polymer was prepared using the procedures described in Example 1, except that the monomer composition was 150 g of butyl acrylate, 340 g of styrene, 500 g of Zonyl ™ and 10 g of methacrylic acid.

Example 11 The polymer was prepared using the procedures described in Example 1, except for a different operator.

Example 12 The polymer was prepared using the procedures described in Example 1, except that the monomer composition was 150 g of butyl acrylate, 340 g of methyl methacrylate, 500 g of Zonyl TAN and 10 g of methacrylic acid.

Example 13 The polymer was prepared using the procedures described in Example 1, except that the monomer composition was 90 g of butyl acrylate, 200 g of styrene, 700 g of Zonyl ™ and 10 g of methacrylic acid.

Example 14 Monomer Emulsion An emulsion of monomers was prepared by homogenizing an organic mixture at 60 ° C, comprising 990 g of Zonyl ™ and 10 g of methacrylic acid, and an aqueous mixture at 60 ° C comprising 300 g of deionized water and 15 g of the solution of Zonyl FSN. Polymerization. Using the same arrangement described in Example 1, 400 g of deionized water and 10 g of the Zonyl FSN surfactant solution were added to the flask. The contents of the flask were heated to 85 ° C under a nitrogen atmosphere, followed by the addition of 20 g of a 50.3% aqueous solution of the methyl-b-cyclodextrin and 20 g of deionized rinse water. Then 35.5 g of the monomer emulsion described above and a buffer solution of 3.5 g of sodium carbonate and 20 g of deionized water were added to the flask. After 2 minutes of stirring, an initiator solution of 2 g of ammonium persulfate and 20 g of deionized water was added to the flask. An exothermic reaction of about 2 ° C was usually observed after the addition of the initiator solution. Approximately 10 minutes after the temperature peak of the exothermic reaction, the remainder of the monomer emulsion and a second initiator solution of 1 g of ammonium persulfate and 50 g of deionized water were gradually added to the flask for a period of 60 minutes. , while the temperature was maintained at 81 ° C. The contents of the flask were maintained at 81 ° C for an additional 15 minutes, after completing the charges, and then cooled to 50 ° C. During cooling, 1 g of a 0.1% ferrous sulfate solution was added to the flask at 70 ° C, followed by 0.3 g of a 70% t-butyl hydroperoxide solution, in admixture with 10 g of water deionized and 0.15 g of sodium sulfoxylate formaldehyde, dissolved in 10 g of deionized water, were added separately. At 50 ° C, another 0.3 g of the t-butyl hydroperoxide solution in admixture with 10 g of deionized water and another 0.15 g of sodium sulfoxylate formaldehyde, dissolved in 10 g of deionized water, were added separately. flask. The final emulsion was then neutralized to a pH of 8 with the addition, in drops, of an ammonium hydroxide solution. The neutralized emulsion was then filtered through a 60 mesh and 325 mesh screen.

The data in Table 2 are percentages by weight, based on the total amount of the monomer. TABLE 2 It can be seen from the above data that a range of amounts of monomers and surfactants can be accommodated in the present invention. The above data also shows that a fluorinated polymer can be prepared in the absence of a fluorinated surfactant without introducing organic solvents or compatibilizers into the polymer latex.

Example 15 Fabrics treated with fluorinated emulsion polymers, prepared according to the method of the present invention, were tested for water moisture resistance. The polymer of Example 4 and a non-fluorinated acrylic binder, commercially available, the Rhoplex® ST-954 binder (trademark of Rohm and Haas Company), were evaluated in water repellency on a nylon fabric, using a standard test method. The treated nylon samples were prepared as follows. A 10 weight percent aqueous dispersion of the emulsion polymer was prepared. This binder formulation was filled on a Birch Brothers cushion, at a pressure of 1.72 x 105 Pa and a speed of 8.23 meters / minute. The sample was dried in an oven at 150 ° C for 4 minutes. The amount of binder added to the nylon samples was approximately 6 weight percent.

The filled samples were evaluated using AATCC Test Method 22-1980, Water Repellency Spray Test. An Indian "0" classification complete wetting of all upper and lower surfaces; a rating of "90" indicates a slight, random upper surface wetting; and a rating of "100" indicates that there is no wetting of the upper surface. The results of the spray test are shown below.

These data indicate that fluorinated emulsion polymers are useful in repelling water from tissues.

Example 16 Slabs treated with a coating containing the fluorinated emulsion polymers, prepared according to the method of the present invention, were tested in water repellency. Six samples, labeled 16-1 to 16-6 and a comparative sample, labeled 16-C, were prepared according to the following table. The comparative sample 16-C was prepared from a commercially available non-fluorinated acrylic binder, the Acryloid® B-66 binder (a trademark of Rohm and Haas Company). A coating of each sample was applied by brush in slabs of Saltillo, Mexico. Each slab was then tested for water penetration, listed by water, watermarks and brightness, and compared to an untreated slab. The results are shown in the following table. The penetration of water was the time, in hours, for water to penetrate the coating. Water listing was classified on a scale of 1 to 10, 1 being the worst and 10 being better. The watermark and brightness were determined by visual inspection.

From the above data, it can be seen that the coatings containing the fluorinated emulsion polymers offer greater gloss, greater resistance to water penetration and a water-enhanced listing, compared to uncoated slabs or slabs coated with an coating of a non-fluorinated polymer.

Claims (10)

1. CLAIMS 1. A method for preparing an emulsion fluorinated polymer, comprising, as polymerized units, at least one fluorinated monomer and at least one non-fluorinated monomer having high water solubility, this method comprises the steps of: a) supplying a reaction mixture, comprising: i) water, ii) a surfactant, iii) a mixture of monomers comprising from 1 to 99 weight percent of at least one fluorinated monomer, from 1 to 10 weight percent of at least one non-fluorinated monomer, which has high solubility in water and 0 to 98 weight percent of at least one non-fluorinated monomer, which has low water solubility, iv) a macromolecular organic compound, which has a hydrophobic cavity and b) polymerizing the monomer mixture.
2. 2. The method of claim 1, wherein the fluorinated monomer is selected from the group consisting of fluoroalkyl (meth) acrylate; fluoroalkylsulfoamidoethyl (meth) acrylate, fluoroalkyl amidoethyl (meth) acrylate; fluoroalkyl (meth) acrylamide; fluoroalkylpropyl (meth) acrylate; (meth) acrylate of fluoroalkylethyl poly (alkylene oxide); fluoro-alkylsulfoethyl (meth) acrylate; fluoroalkylethyl vinyl ether; fluoroalkyl-ethyl-poly (ethylene oxide) -vinyl ether; pentafluoro-styrene; fluoroalkyl-styrene; fluorinated α-olefins; perfluoro-butadiene; 1-fluoroalkylperfluorobutadiene; di (meth) acrylate of aH, H,? H,? H-perfluoroalkanediol; and β-substituted fluoroalkyl (meth) acrylate.
3. 3. The method of claim 1, wherein the fluorinated monomer is selected from perfluorooctylethyl (meth) acrylate and perfluorooctylethyl acrylate.
4. 4. The method of claim 1, wherein the macromolecular organic compound is selected from the group consisting of cyclodextrin; cyclodextrin derivatives; cycloinulohexose; cycloinuloheptose; cycloinulooctosa, calixareno and cavitandos.
5. 5. The method of claim 1, wherein the non-fluorinated monomer, which has high solubility in water, is selected from the group consisting of monoethylenically-α-unsaturated monomers, which contain acid functionality; (meth) acrylates substituted with sulfoethyl acid and methacrylate; (meth) acrylamides substituted with acid; (meth) acrylates substituted with bases and (meth) acrylamides; acrylonitrile; (meth) acrylamide and substituted (meth) acrylamide; (met) croleína; and methyl acrylate.
6. 6. The method of claim 1, wherein the non-fluorinated monomer having low water solubility is selected from the group consisting of α, β-unsaturated ethylenically, styrene and styrene-alkyl-substituted monomers; α-methyl styrene; vinyl toluene; vinyl esters of carboxylic acids (C4-C30); vinyl chloride; vinylidene chloride; N-alkyl-substituted (meth) acrylamide, violinyl-alkyl or aryl ethers with (C3-C30) alkyl groups; esters of (C 1 -C 30) alkyl of (meth) acrylic acid; unsaturated vinyl esters of (meth) acrylic acid; multifunctional monomers and monomers derived from cholesterol.
7. 7. The method of claim 1, wherein the molar ratio of the macromolecular organic compound to the fluorinated monomer is from 5: 1 to 1: 5000.
8. 8. The method of claim 1, wherein the surfactant is selected from the group consisting of a non-fluorinated anionic surfactant, a non-fluorinated nonionic surfactant, a fluorinated anionic surfactant, a fluorinated nonionic surfactant and mixtures thereof.
9. 9. A composition comprising a macromolecular organic compound and an emulsion fluorinated polymer, comprising, as polymerized units, from 1 to 99 weight percent of at least one fluorinated monomer, from 1 to 10 weight percent of at least one monomer non-fluorinated, having a high solubility in water, and 0 to 98 weight percent of at least one non-fluorinated monomer, which has low water solubility.
10. 10. An article comprising a coated substrate, wherein the coating includes the composition of claim 9.