US3576018A - Acrylyl derivatives of fluorinated amides - Google Patents

Acrylyl derivatives of fluorinated amides Download PDF

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US3576018A
US3576018A US749310A US3576018DA US3576018A US 3576018 A US3576018 A US 3576018A US 749310 A US749310 A US 749310A US 3576018D A US3576018D A US 3576018DA US 3576018 A US3576018 A US 3576018A
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acrylyl
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Richard F Sweeney
Alson K Price
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Allied Corp
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/408—Acylated amines containing fluorine atoms; Amides of perfluoro carboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids

Definitions

  • Acrylyl derivatives of fluorinated amides useful as oiland water-repellency agents have the structural formula wherein x and y are integers from 2 to 6 and 1 to 4, respectively; wherein R is a perfluoroalkyl or a fluorinated isoalkoxyalkyl radical; Z is H, alkyl, hydroxyalky, a fluorinated acyl radical R CO wherein R is as described above, or an acrylyl radical; Z is H, alkyl, hydroxyalky, a fluorinated acyl radical R;CO wherein R is as described above, an acrylyl radical or a radical having the formula C H NHZ wherein Z is as described above, there being at least one fluorinated acyl radical R CO- and at least one acrylyl radical in the molecule represented by Z and/ or Z.
  • This invention is directed to a new class of fluorocarbon derivatives and to their application to fibrous materials such as textiles and paper to produce oiland water-repellent products. More particularly, this invention relates to reaction products of fluorinated polyamide compounds with acid halides of tat-unsaturated carboxylic acids, to treatment of textile, paper and other fibrous materials therewith to render the same oleophobic and hydrophobic, and to textile, paper and other fibrous products treated therewith so as to have been rendered oiland water-repellent.
  • fluorochemicals in the treatment of textile, paper and other fibrous products to impart thereto oiland water-repellency properties.
  • these fluorochemicals are composed of a fluorinated alkyl chain aflixed to an active functional group.
  • the oleophobic and hydrophobic properties of the fluoro chemicals are attributed, at least in part, to the inherent low surface energy of the fluorinated surface provided by the fluorinated alkyl chain.
  • the portion of the molecule to which the fluorinated alkyl chain is affixed provides the physical and chemical bond between the fluorinated alkyl chain and the substrate surface.
  • This bond not only influences the degree of orientation and packing of the fluorinated groups of the fluorinated alkyl chain, and hence, the oiland water-repellency properties of the fluorochemical, but in particular, determines the durability of the oleophobic and hydrophobic properties obtained.
  • one object of the present invention is the provision of novel fluorocarbon derivatives.
  • Another object is to provide oiland water-repellent compositions of novel fluorocarbon derivatives suitable for treating fibrous materals, such as paper and textiles, to impart thereto oleophobic and hydrophobic properties.
  • a still further object is to provide methods for the treatment of textiles, paper and other fibrous products, employing said fluorocarbon derivatives.
  • a further object is to provide textile and paper materials treated with the fluorocarbon derivatives of the present invention.
  • reaction products of fluorinated polyamide compounds with acid halides of certain tat-unsaturated carboxylic acids have been found to impart to textiles, paper and other fibrous products durable oiland water-repellency properties.
  • Rf is a radical selected from the group consisting (a) perfluoroalkyl having from 3 to 17 carbon atoms, and (b) a radical having the formula wherein (i) R and R are fluorine or are fluoroalkyl groups, or when taken together, are fluoroalkylene groups forming a cycloaliphatic structure, which R and R groups may each have from 1 to 9 carbon atoms, provided that not more than three of the R and R groups may be fluoroalkyl groups, (ii) m and n are each integers of from 0 to 20, with the proviso that the sum of m and n is from 0 to 20, and provided further that when r is 0, m is at least 1, (iii) X is selected from the group consisting of hydrogen and fluorine, with the proviso that when n is greater than 0, then X is always hydrogen, (iv) p is 0 to 1, (v) r is O or 1, with the proviso that when the sum
  • acyl groups is a member selected from the group consisting of (a) hydrogen, (b) alkyl having from 1 to 6 carbon atoms, (c) a radical having the formula ROH wherein R is a divalent alkylene bridging group containing from 1 to 6 carbon atoms, (d) a fluorinated acyl radical having the formula i C-Rt wherein R; has the afore-stated meaning,
  • novel fluorocarbon derivatives of the present invention are prepared by reacting a fluorinated polyamide starting material as hereinbelow defined with an u-unsaturated acyl halide reactant at temperatures between about 0 C. to about 160 C., preferably in the presence of an inert organic solvent.
  • acyl halide reactants employed in the preparation of the novel fluorocarbon derivatives of the present invention are known compounds which are represented by the formula 'wherein R, R and R are independently selected from the group consisting of H and alkyl having from 1 to 6 carbon atoms, and wherein A is a halogen selected from the group consisting of F, Cl, Br and I.
  • Acrylyl chloride methacrylyl fluoride, 2,3,3-trihexylacrylyl fluoride, 3,3-dihexylmethacrylyl chloride, 3butyl-Bethyl-B-propylacrylyl iodide, 3-propyl-3ethyl-methacrylyl fluoride, 3-hexyl- 3-ethylacrylyl chloride, 2,3-dihexylacrylyl bromide, 3- amylacrylyl fluoride, 3,3-diethylacrylyl fluoride, 3-ethyl-2- hexylacrylyl bromide, 3-ethylmethacrylyl chloride and 3,3-diethylmethacrylyl chloride are illustrative of a-unsaturated acyl halide reactants suitable for making novel fluorocarbon compounds of the present invention.
  • x is as stated above and Y is a fluorinated acyl radical, said fluorinated acyl radical having the aforestated formula, and at least one of Y or Y is hydrogen.
  • the fluorinated polyamide reactant of Formula II, above IS prepared by reaction of a fluorinated carboxylic acid having the formula R COOH wherein R, has the afore-stated meaning, or a derivative thereof, such as an ester, anhydride or acid halide thereof with a polyalkylene polyamine compound corresponding to the general formu a NH: o xHarl n yC xHaNHQ wherein x and y have the afore-stated meanings; wherein Q is selected from the group consisting of hydrogen, alkyl having from 1 to 6 carbon atoms, and a radical having the formula ROH wherein R has the afore-stated meanmg; and wherein Q is selected from the group consisting of hydrogen, alkyl having from 1 to 6 carbon atoms, a radical having the formula ROH wherein R has the afore-stated meaning, or an aminoalkyl radical having the formula C H NHQ wherein x and Q have the afor
  • polyalkylene polyamines employable herein include diethylene triamine, di r1 propylene triamine, di-butylene triamine, di-n-hexylene triamine, triethylene tetramine, tri-i-propylene tetramine, tri n hexylene tetramine, 4- (2 aminoethyl) 1,4,7 triazaheptane, tetraethylene pentamine, tetra n propylene pentamine, tetra-n-butylene pentamine, 4 (2 aminoethyl) 1,4,7,l tetraazadecane, tetra n hexylene pentamine, pentaethylene hexamine, 1 (hydroxyethyl)
  • Fluorinated carboxylic acid reactants above described, wherein R is perfluoroalkyl, suitable for reaction with the above polyalkylene polyamine reactants are saturated straight-chain or branched-chain monocarboxylic acids or stated derivatives thereof containing from 4 to 18 carbon atoms in the acid portion of the molecule. Discrete molecular species of the perfluorocarboxylic acid reactants may be used or mixtures of these reactants in various proportions having the indicated carbon chain length may be employed.
  • Illustrative perfiuorocarboxylic acid reactants include perfluorobutyric, perfiuorocaproic, perfluorocaprylic, perfluorolauric, perfluoromyristic, perfluoropalmitic, and perfluorostearic acids, as well as various isomeric forms thereof.
  • Perfluorocarboxylic acid reactants herein contemplated containing up to about ten carbon atoms are readily prepared by the electrochemical fluoroination of alkanoic acids in anhydrous hydrogen fluoride with subsequent hydrolysis of the resulting fluorinated acid fluorides, as disclosed in US. Pat. 2,567,011, issued Sept. 4, 1951.
  • Longer chain perfluorocarboxylic acid reactants, i.e. those containing from about 11 to 18 carbon atoms, may be obtained by reaction of perfluoroalkyl iodides with oleum containing about 15% to 45% sulfur trioxide at elevated temperatures followed by hydrolysis of the resulting perfluorocarboxylic acid fluoride, as disclosed in French Pat. 1,343,601 of Oct. 14, 1963.
  • Fluorinated carboxylic acid reactants above described, wherein R, is a radical having the formula wherein R R X, r, n, m and p have the afore-stated meanings may be prepared by various hereinafter described methods.
  • Fluorinated carboxylic acids of the formula R COOH wherein R; has the Formula IV, above, wherein m is at least 1 and the sum of n and p is at least 1, can be prepared from telomers having the general formula wherein R and R have the afore-stated meanings, wherein s and t are each integers from 0 to 20, the sum of s and I being at least 1, and wherein E is a halogen selected from the group consisting of Br and I.
  • Telomers of that type and their preparation are described in commonly assigned copending application of Anello et al. entitled, Telomers and Process for the Preparation Thereof, Ser. No. 633,359, filed Apr. 25, 1967 now U.S. Pat.
  • telomers are prepared by radical addition reactions of polyfluoroisoalkoxyalkyl halide telogens of the formula wherein R R and E have the afore-stated meanings, with telomerizable unsaturated compounds.
  • the telomerization reaction may be initiated by heat or by means of a free radical initiating catalyst.
  • the polyfluoroisoalkoxyalkyl halide telogen starting materials may be prepared by reacting a corresponding halogenated ketone with an ionizable flouride salt, e.g.
  • telogen starting materials are described in detail in copending applications of Litt et al., Fluorinated Ethers, U.S. Ser. Nos. 492,276 and 513,574, filed Oct. 1, 1965, and Dec. 13, 1965, respectively now US. Pats. 3,453,333 and 3,470,256 respectively, the pertinent subject matter of which applications is hereby incorporated by reference.
  • Fluorinated carboxylic acids of the formula R COO'H wherein R has the Formula IV, above, wherein r, n and p are all 0 and wherein m is at least 2 may be prepared by reacting the corresponding telomer represented by general Formula V, above, wherein t is 0 with ICN or (CN) to form the nitrile, followed by hydrolysis of the nitrile in known manner to form the free acid.
  • the reaction between the telomer and the ICN or (CN) to form the nitrile is carried out under superatmospheric pressure above about 20 to 200 atmospheres or more at temperatures in excess of about 300 C., preferably using an excess of the ICN or (CN) reactant.
  • Hydrolysis of the nitrile to form the free acid can be effected by treatment with aqueous mineral acid, such as hydrochloric, phosphoric, or sulfuric acid, at temperatures between about 60 and about 125 C.
  • Fluorinated carboxylic acids of the formula R COOI-I wherein R has the Formula IV, above, wherein m is at least 1, p and r are both 0 and n is greater than 0 may be prepared by reacting the corresponding telomer represented by Formula V, above, wherein t is greater than 0 with an alkali metal cyanide to form the nitrile, followed by hydrolysis of the nitrile to form the free acid, as described above.
  • the reaction between the telomer and the alkali metal cyanide is preferably carried out in aqueous alcoholic solution at temperatures between about 60 and about C.
  • Fluorinated carboxylic acids of the formula R COOH wherein R has the Formula IV, above, wherein m is at least 1, r is O, p is l and X is hydrogen can be prepared by reacting the corresponding telomer represented by general Formula V, above, wherein t is at least 1 with S0 to form the corresponding pyrosulfate, or with oleum to form the corresponding hydrosulfate, hydrolysis of the pyrosulfate or the hydrosulfate with aqueous acid to form the corresponding alcohol, followed by oxidation of the alcohol with dichromate, permanganate or strong nitric acid to form the free acid.
  • Fluorinated carboxylic acids of the formula R COOH wherein R, has the Formula IV, above, where m is at least 1, r and n are both 0, p is 1 and X is fluorine can be prepared by reacting a corresponding telomer represented by Formula V, above, wherein t is with $0 to form corresponding acid halides and halopyrosulfates, and hydrolyzing the acid halides and halopyrosulfates by refluxing with water to obtain the corresponding free acids.
  • Fluorinated carboxylic acids of the formula R COOH wherein R: has the Formula IV, above, wherein r is 1 and m, n and p are all 0 can be prepared by the same method from polyfluoroisoalkoxyalkyl halide compounds of Formula VI, above.
  • Fluorinated carboxylic acids of the formula R COOH wherein R; has the Formula IV, above, wherein mis 1 and r, n and p are all 0 can be prepared from polyfluoroisoalkoxyalkyl halide compounds of Formula VI, above, by reacting them with a Grignard reagent to form a magnesium halide adduct, reacting this adduct with CO to form a magnesium halide salt, and then acidifying the salt to obtain the desired acid.
  • the reactions involving the Grignard reagent and the carbon dioxide proceed very rapidly and can be conducted at tempera tures considerably below 0 C.
  • esters and acid halides of the above-described acids may be prepared from the acids by conventional procedures.
  • telomers of Formula V, above, and the fluorinated carboxylic acid reactants derived therefrom may be prepared as discrete compounds, they are generally obtained as mixtures of compounds of varying chain length. It is to be understood that both, the individual discrete fluorinated carboxylic acid reactants as well as their mixtures of compounds of varying chain length are suitable for the preparation of the fluorinated polyamide compounds employed in the preparation of the compounds of the present invention.
  • the fluorinated polyamide reactants of Formula II, above may be prepared by simply mixing the fluorinated carboxylic acid reactant with the polyalkylene polyamine Starting material of Formula III, above. These reactants may be charged in a molar proportion of 1 mol of polyalkylene polyamine to about 1 to 7 mols of fluorinated carboxylic acid reactant. If desired, the reaction may be carried out in the presence of a suitable inert organic solvent. Suitable reaction temperatures range between about 0 C. to about 200 C. Upon conclusion of the reaction, the desired fluorinated polyamide compound may be recovered from the reaction mixture by methods known to those skilled in the art.
  • the reaction product obtained as a result of the reaction of the fluorinated carboxylic acid reactant and the polyalkylene polyamine reactant above described, may comprise a single compound conforming to the above stated structural Formula II, a mixture of isomers thereof or a reaction mass composed of amide products containing two or more amide functions depending upon the polyalkylene polyamine reactant employed, the reactivity of the fluorinated carboxylic acid reactant present, the solubility of the amide product obtained during the reaction in the reaction mixture and the molar proportions of fluorinated carboxylic acid reactant employed.
  • the resulting fluorinated polyamide product whether it comprises a single compound, a mixture of isomers thereof or a mass composed of amide products containing tWo or more amide functions, is suitable without further purification for reaction with the wunsaturated acyl halide reactant, above described, to form the fluorocarbon derivatives of the present invention.
  • the fluorinated polyamide may be further purified prior to reaction with the tar-unsaturated acyl halide reactant, as by distillation or recrystallization using any commonly employed inert organic solvent such as acetonitrile or chloroform.
  • novel fluorocarbon derivatives of this invention are prepared by reacting the a-unsaturated acyl halide reactant with the fluorinated polyamide starting material, above described. These reactants may be charged in a mol proportion of 1 mol of fluorinated polyamide to about 1 to 10, preferably about 2 to 4, mols of tat-unsaturated acyl halide reactant. Reaction temperature and time are dependent upon the particular fluorinated polyamide and zit-unsaturated acyl halide reactants involved. The temperature ranges from about 0 C. to about 160 C., preferably about 10 C. to about C. The reaction is quite rapid even at about room temperature.
  • Reaction times generally range between about 10 minutes and about 4 hours. If desired, the reaction may be conducted in the presence of an inert organic solvent and, when present, the maximum temperature employable is limited only by the reflux temperature of the reaction mixture. Although the reaction may be carried out under superatmospheric pressure, it is preferred to conduct the reaction at atmospheric pressure.
  • the desired product can be extracted from the reaction mixture using a suitable solvent, such as ether, acetone, acetonitrile, and the like, and can be purified, as e.g. by fractional crystallization.
  • a suitable solvent such as ether, acetone, acetonitrile, and the like
  • the reaction is carried out in an acetone medium.
  • Acetone dissolves the starting ma terials and the desired product, but not the by-product halide salt.
  • recovery of the desired product is facilitated in that, upon completion of the reaction, the reaction, the by-product halide salt can be simply removed by filtration of the reaction mixture.
  • the halide salt by-product can be reconverted to the fluorinated polyamide starting material in known manner by treatment with an appropriate ion exchange resin or with an aqueous base, such as aqueous sodium hydroxide.
  • the reaction it is preferred to conduct the reaction in the presence of one of the Well known free radical inhibitors, such as u-pinene.
  • the free radical inhibitor if one is used, is employed in amount of between 0.01% to about 1.0% by weight, based on the total Weight of the reaction mixture.
  • the reaction is preferably carried out in the presence of an acid-interceptor, such as sodium bicarbonate, to thereby increase the yield of the desired product and to reduce the amount of by-product halide salt formed in the reaction.
  • an acid-interceptor such as sodium bicarbonate
  • the reaction is preferably carried out under exclusion of water using anhydrous reagents.
  • the alkylene linkage (C H in the novel compounds of the present invention may be a straight-chain or branched-chain group, preferably containing from 2 to 4 carbon atoms.
  • R groups in the novel fluorocarbon derivatives of the present invention represented by Formula I, above, may be the same or different.
  • the R; group is a perfluoroalkyl group, it may be straight-chain or branchedchain, preferably containing from 6 to 14 carbon atoms.
  • R and R are preferably fluorine or perfluoroalkyl groups.
  • R, and R preferably contain 1-2 carbon atoms.
  • the atomic ratio of fluorine to hydrogen is at least 1: 1.
  • integer m in the Rf radical of Formula IV, above is at least 1, and the sum of m and n is preferably from 1 to 10.
  • Specific examples of preferred embodiments of the preferred moiety of the R radical of the compounds of the present invention include the following:
  • R R R R and y have the aforestated mean ings and x is an integer from 2 to 4 constitute preferred embodiments of the present invention, those wherein R is selected from the group consisting of H and methyl, and wherein R and R are independently selected from the group consisting of H and alkyl having from 1 to 2 carbon atoms being more preferred yet.
  • Acrylyl and methacrylyl 10 radicals are specific examples of preferred tit-unsaturated acyl radicals.
  • a specific class of preferred embodiments of the present invention are compounds according to Formula VII, above, wherein the R; radical has the formula wherein m is an integer from 1 to 10, n is an integer from 0 to 10, with the proviso that the sum of m and n is from 1 to 10, and wherein X and p have the aforestated meanings.
  • the crude product is twice recrystallized from acetonitrile to yield about 20 g. of the colorless solid product, 1,7-bis- (perfluorooctanoyl)-4-acrylyl-2,4,7 triazaheptane, having the formula A portion of that product is subjected to further recrystallization from acetonitrile to yield an analytical sample (M.P. 115116 0.).
  • the 1,7-bis (perfluorooctanoyl) -1,4,7-triazaheptane reactant is prepared in the following manner:
  • a solution of 49 grams (0.475 mol) of diethylene triamine in 60 ml. of diethyl ether is placed in a reaction vessel equipped with a dropping funnel, condenser, magnetic stirrer and a calcium chloride drying tube. After chilling the vessel in an ice water bath for a period of about 20 minutes, 34.2 grams (0.079 mol) of n-perfluorooctanoyl chloride is added with stirring to the contents of the vessel during a 30 minute period. After addition of the n-perfluorooctanoyl chloride reactant is complete, the ice water bath is removed and the stirring is continued at room temperature for a period of 20 minutes. Thereafter ml.
  • the oiland water-repellent compounds of the invention are useful in treating paper as Well as textiles (fabrics and fibers) comprised of natural or synthetic fibers including cotton, nylon, wool, polyethylene terephthalate and polyacrylonitrile.
  • the fluorocarbon derivatives of the invention are especially useful in the treatment of fabrics and fibers comprised of cellulosic and certain cellulosic derivatives which contain cellulosic hydroxyl groups such as cotton, linen, viscose, cupra ammonium rayon, saponified cellulose acetate and salts of cellulose xanthate.
  • the invention is also applicable to the treatment of blends of natural and/or synthetic fibers in cloth, for example, blends containing polyethylene terephthalate, polyacrylonitrile, nylon, cotton and wool.
  • auxiliary agents such as those imparting water repellency, crease resistance and softening properties may be applied in conjunction with the fluorocarbon chemicals of the invention.
  • other materials such as the surfaces of wood, plastics, glass and metals may be treated with solutions or suspensions containing the fluorocarbon derivatives of the invention to render the same oiland water-repellent.
  • the fluorocarbon derivatives of the present invention may be applied to the article to be rendered oiland water-repellent by treating the same with a solution of the repellent and evaporating the solvent. If desired, the treated article may then be cured at an elevated temperature.
  • the concentration of the fluorocarbon derivative on the treated article generally may vary from about 0.5% to preferably 1.0% to 4.0%, based on the weight of the article. Since the solvent used in formulating the oiland Water-repellent composition functions essentially as a carrier for the fluorocarbon derivative, any organic liquid inert to the article to be treated and capable of dissolution of the requisite amount of oiland Water-repellency agent may be employed.
  • Acetone, methyl ethyl ketone, acetonitrile and dimethylformamide are illustrative solvents which may be used in preparing the oiland water-repellent compositions.
  • aqueous emulsions of the oiland water-repellent may be applied onto the articles to be treated by conventional aqueous application methods.
  • the solvent may be evaporated by air drying at room temperature. If it is desired to cure the treated articles the solvent may be evaporated prior to curing or during curing of the oiland water-repellent chemical onto the article.
  • the article treated with a solution of the fluorocarbon derivative is air dried prior to curing for a time suflicient to evaporate essentially all of the solvent. Thereafter, the article having on its surface the oiland water-repellent chemical is cured or heat-set at a temperature of about 100 C. to 160 C. for a time period varying inversely with the temperature, ranging from about 1 second to 5 minutes.
  • the fluorocarbon derivatives of the present invention are preferably applied thereto from an aqueous solution or an aqueous emulsion and in the presence of a catalyst of the type commonly used as crosslinking catalyst for crosslinking resins with cellulosic materials.
  • the fluorocarbon derivatives of the present invention respond equally Well to basic as well as acidic catalysts, thus, have the decided advantage that their use is compatible with permanent press treatment, which treatment commonly employs acidic reactants.
  • the cellulosic material is moistened with an aqueous solution of the catalyst, air dried to remove residual Water and then impregnated with an aqueous solution or emulsion of the fluorocarbon derivative of the invention for a time, normally 30 seconds to about 30 minutes, sufficient to retain on the cellulosic material about 1 to 10%, preferably 2 to 4% of the fluorocarbon derivative, based on the weight of the cellulosic material.
  • the thusly impregnated cellulosic material is then heated at a temperature of C. to C. for a time period varying inversely with the temperature ranging from about 15 minutes to 30 seconds.
  • the chemically modified cellulosic material is Washed free of excess catalyst with water and dried.
  • the cellulosic material may be first impregnated with an aqueous solution or emulsion of the fluorocarbon derivative, then treated with an aqueous solution of the catalyst, air dried and finally heated to effect reaction of the fluorocarbon derivative With the cellulosic material.
  • Another modification of the above-described procedure involves premixing the aqueous solution or emulsion of the fluorocarbon derivative together With the catalyst prior to impregnation of the cellulosic material.
  • suitable basic catalysts should have a dis association constant in water of at least 1.8)(10 at 25 C.
  • Phosphates, carbonates and hydroxides of alkali metals such as sodium phosphate, sodium carbonate, sodium hydroxide and potassium hydroxide; alkaline-earth metal hydroxides including calcium hydroxide and magnesium hydroxide; and quaternary ammonium hydroxides such as tetraethyl ammonium hydroxide and benzyl trimethyl ammonium hydroxide are illustrative of preferred effective basic catalysts.
  • Suitable acid catalysts are the mineral acids and strong organic acids, as well as the ammonium salts, amine salts and metal salts of strong acids.
  • the salts of strong acids are preferred acid catalysts, ammonium chloride, magnesium chloride, zinc nitrate and zinc chloride being specific examples of preferred acid catalysts.
  • the catalyst concentration is normally dependent upon the strength of the acid or base catalyst selected, speed of reaction desired and the nature of the cellulosic material to be treated. In general, catalyst concentrations of about 1 to 20%, preferably 2 to 5%, based on the Weight of the solution are satisfactory.
  • Wash fastness of the treated cloth was determined by subjecting the cloth to repeated launderings in hot wat r in a household automatic washing machine using a heavy duty detergent, followed by drying in an automatic drier. The material was ironed prior to testing.
  • test pieces Same as in (a) above, except that prior to impregnation with the acetone solution of the fluorocarbon compound the test pieces were totally immersed in a 5% aqueous magnesium chloride solution, were wrung out, and were then dried at 80 C. for 8 minutes.
  • test pieces Same as in (a) above, except that prior to impregnation with the acetone solution of the fluorocarbon cornpound the test pieces were totally immersed in a 5% aqueous sodium hydroxide solution, were wrung out, and were then dried at 80 C. for 8 minutes.
  • test specimens pieces of 80 x 80 count white cot- TABLE III ton print cloth, spun 100% Nylon cloth, Type 54 Dacron (T.M.)/cotton blend poplin weight cloth, were treated oasto r oil, Tollllene, Heptane, with a 1.75 percent solution of 1,7-bis (perfluorooctanoyl)- 65 ume Wlum" 4-acrylyl-1,4,7-triazaheptane in acetone as follows: 200 0 o (a) The test specimens were impregnated by total un- 1: "j: 180 10 10 mersion in the acetone solution of the fluorocarbon com- E3 g3 g8 pound for 3 minutes.
  • the specimens were then dried at 120 40 40 80 C. for two minutes, and were then heated in an oven 70 lgg 2g 58 at C. for four minutes.
  • the speci- 60 70 s mens were washed in warm water, dried at 80 C. for 10 g3 3g 88 minutes, ironed, and conditioned at 50% RH. After each 0 100 3 laundering the test pieces were likewise subjected to iron- 0 90 110 ing and conditioning of 50% RH. 75
  • Papers having a Kit Number of about 5-6 or below will exhibit only fair oil-repellency; those papers having 8. Kit Number of about 8-10 will have good oil-repellency, and those having a Kit Number of about 10 and up will have excellent oil-repellency.
  • R is a radical selected from the group consisting of (a) perfluoroalkyl having from to 15 carbon atoms, and
  • X is selected from the group consisting of hydrogen and fluorine, with the proviso that when n is greater than 0, then X is always hydrogen,
  • r is 0 or 1, with the proviso that when the sum of m, n and p is greater than 0, then r is alw y 0;
  • R R and R are independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms.
  • R is a perfluoroalkyl radical having from 6 to 14 carbon atoms.
  • R" is selected from the group consisting of hydrogen and methyl, and wherein R and R are independently selected from the group consisting of hydrogen and alkyl having from 1 to 2 carbon atoms.
  • R is selected from the group consisting of hydrogen and methyl and wherein R and R are independently selected from the group consisting of hydrogen and alkyl having from 1 to 2 carbon atoms.
  • a compound aCcOrding to claim 11 having the structural formula [(CF CFO(CF CONHC H N COCH CH 13.

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Abstract

WHEREIN X AND Y ARE INTEGERS FROM 2 TO 6 AND 1 TO 4, RESPECTIVELY; WHEREIN RF IS A PERFLUOROALKYL OR A FLUORINATED ISOALKOXYALKYL RADICAL; Z IS H, ALKYL, HYDROXYALKY, A FLUORINATED ACYL RADICAL RFCO- WHEREIN RF IS AS DESCRIBED ABOVE, OR AN ACRYLYL RADICAL; Z'' IS H, ALKYL, HYDROXYALKY, A FLUORINATED ACYL RADICAL RFCO- WHEREIN RF IS AS DESCRIBED ABOVE, AN ACRYLYL RADICAL OR A RADICAL HAVING THE FORMULA -CXH2XNHZ WHEREIN Z IS AS DESCRIBED ABOVE, THERE BEING AT LEAST ONE FLUORINATED ACYL RADICAL RFCO- AND AT LEAST ONE ACRYLYL RADICAL IN THE MOLECULE REPRESENTED BY Z AND/OR Z''.

RF-CO-NH-(CXH2X-N(-Z''))Y-CXH2X-NH-Z

ACRYLYL DERIVATIVES OF FLUORINATED AMIDES USEFUL AS OILAND WATER-REPELLENCY AGENTS HAVE THE STRUCTURAL FORMULA

Description

3,576,018 ACRYLYL DERIVATIVES OF FLUORINATED AMIDES Richard F. Sweeney, Randolph Township, Morris County, and Alson K. Price, Morris Township, Morris County, N.J., assignors to Allied Chemical Corporation, New York, N.Y. No Drawing. Filed Aug. 1, 1968, Ser. No. 749,310 Int. Cl. C09f 7/00 US. Cl. 260-4045 13 Claims ABSTRACT OF THE DISCLOSURE Acrylyl derivatives of fluorinated amides useful as oiland water-repellency agents have the structural formula wherein x and y are integers from 2 to 6 and 1 to 4, respectively; wherein R is a perfluoroalkyl or a fluorinated isoalkoxyalkyl radical; Z is H, alkyl, hydroxyalky, a fluorinated acyl radical R CO wherein R is as described above, or an acrylyl radical; Z is H, alkyl, hydroxyalky, a fluorinated acyl radical R;CO wherein R is as described above, an acrylyl radical or a radical having the formula C H NHZ wherein Z is as described above, there being at least one fluorinated acyl radical R CO- and at least one acrylyl radical in the molecule represented by Z and/ or Z.
BACKGROUND OF THE INVENTION This invention is directed to a new class of fluorocarbon derivatives and to their application to fibrous materials such as textiles and paper to produce oiland water-repellent products. More particularly, this invention relates to reaction products of fluorinated polyamide compounds with acid halides of tat-unsaturated carboxylic acids, to treatment of textile, paper and other fibrous materials therewith to render the same oleophobic and hydrophobic, and to textile, paper and other fibrous products treated therewith so as to have been rendered oiland water-repellent.
It is known to employ certain fluorochemicals in the treatment of textile, paper and other fibrous products to impart thereto oiland water-repellency properties. In general, these fluorochemicals are composed of a fluorinated alkyl chain aflixed to an active functional group. The oleophobic and hydrophobic properties of the fluoro chemicals are attributed, at least in part, to the inherent low surface energy of the fluorinated surface provided by the fluorinated alkyl chain. The portion of the molecule to which the fluorinated alkyl chain is affixed provides the physical and chemical bond between the fluorinated alkyl chain and the substrate surface. This bond not only influences the degree of orientation and packing of the fluorinated groups of the fluorinated alkyl chain, and hence, the oiland water-repellency properties of the fluorochemical, but in particular, determines the durability of the oleophobic and hydrophobic properties obtained.
There is always a need for new oiland water-repellency agents, particularly for those which are not only capable of obtaining high levels of oiland water-repellency, but are also capable of maintaining oleophobic and hydrophobic properties of substrate surfaces treated therewith after their repeated exposure to laundering.
Accordingly, one object of the present invention is the provision of novel fluorocarbon derivatives.
nited States Patent for Another object is to provide oiland water-repellent compositions of novel fluorocarbon derivatives suitable for treating fibrous materals, such as paper and textiles, to impart thereto oleophobic and hydrophobic properties.
A still further object is to provide methods for the treatment of textiles, paper and other fibrous products, employing said fluorocarbon derivatives.
A further object is to provide textile and paper materials treated with the fluorocarbon derivatives of the present invention.
These and other objects will be apparent from the following description.
DESCRIPTION OF THE INVENTION In accordance with the present invention, reaction products of fluorinated polyamide compounds with acid halides of certain tat-unsaturated carboxylic acids have been found to impart to textiles, paper and other fibrous products durable oiland water-repellency properties.
The compounds proposed for use as oiland waterrepellency agents conform to the general formula:
wherein (1) Rf is a radical selected from the group consisting (a) perfluoroalkyl having from 3 to 17 carbon atoms, and (b) a radical having the formula wherein (i) R and R are fluorine or are fluoroalkyl groups, or when taken together, are fluoroalkylene groups forming a cycloaliphatic structure, which R and R groups may each have from 1 to 9 carbon atoms, provided that not more than three of the R and R groups may be fluoroalkyl groups, (ii) m and n are each integers of from 0 to 20, with the proviso that the sum of m and n is from 0 to 20, and provided further that when r is 0, m is at least 1, (iii) X is selected from the group consisting of hydrogen and fluorine, with the proviso that when n is greater than 0, then X is always hydrogen, (iv) p is 0 to 1, (v) r is O or 1, with the proviso that when the sum of m, n and p is greater than 0, then r is always 0, (2) x is an integer from 2 to 6, (3) y is an integer from 1 to 4, (4) Z is a member selected from the group consisting (a) hydrogen, (b) alkyl having from 1 to 6 carbon atoms, (c) a radical having the formula ROH wherein R is a divalent alkylene bridging group containing from 1 to 6 carbon atoms,
(e) an tit-unsaturated acyl radical having the formula in which R, and R and R are independently selected horn the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms, and (5) Z, which may be the same or different in different Z! (o,H2,N)
groups, is a member selected from the group consisting of (a) hydrogen, (b) alkyl having from 1 to 6 carbon atoms, (c) a radical having the formula ROH wherein R is a divalent alkylene bridging group containing from 1 to 6 carbon atoms, (d) a fluorinated acyl radical having the formula i C-Rt wherein R; has the afore-stated meaning,
(e) an tat-unsaturated acyl radical having the formula 0 R /R b-iho in which R R and R have the afore-stated meanings, and (f) a radical having the formula C,H2;NZ
wherein x and Z have the afore-stated meanings, with the proviso that at least one of Z or Z is a fluorinated acyl radical or one of Z is a radical having the formula wherein Z is a fluorinated acyl radical, and at least one of Z or Z is an car-unsaturated acyl radical or one of Z is a radical having the formula H C =H2XII\IZ wherein is an tit-unsaturated acyl radical, said fluorinated acyl radical and (at-unsaturated acyl radical having the afore-stated formulas.
The novel fluorocarbon derivatives of the present invention are prepared by reacting a fluorinated polyamide starting material as hereinbelow defined with an u-unsaturated acyl halide reactant at temperatures between about 0 C. to about 160 C., preferably in the presence of an inert organic solvent.
The a-unsaturated acyl halide reactants employed in the preparation of the novel fluorocarbon derivatives of the present invention, as a class, are known compounds which are represented by the formula 'wherein R, R and R are independently selected from the group consisting of H and alkyl having from 1 to 6 carbon atoms, and wherein A is a halogen selected from the group consisting of F, Cl, Br and I. Acrylyl chloride, methacrylyl fluoride, 2,3,3-trihexylacrylyl fluoride, 3,3-dihexylmethacrylyl chloride, 3butyl-Bethyl-B-propylacrylyl iodide, 3-propyl-3ethyl-methacrylyl fluoride, 3-hexyl- 3-ethylacrylyl chloride, 2,3-dihexylacrylyl bromide, 3- amylacrylyl fluoride, 3,3-diethylacrylyl fluoride, 3-ethyl-2- hexylacrylyl bromide, 3-ethylmethacrylyl chloride and 3,3-diethylmethacrylyl chloride are illustrative of a-unsaturated acyl halide reactants suitable for making novel fluorocarbon compounds of the present invention.
The fluorinated polyamide reactant suitable for reaction with the above a-unsaturated acyl halide reactants is characterized by the structural formula:
Y! R li l 1'- C xII2;1 I) G xHixl lY (II) wherein R x and y have the above-stated meanings; Y is a member selected from the group consisting of hydrogen, alkyl having from 1 to 6 carbon atoms, a radical having the formula ROH wherein R 'has the abovestated meaning and a fluorinated acyl radical having the formula wherein R, has the above-stated meaning; and Y, which may be the same or different in different 'IYI (CXH2XN)- groups, is a member selected from the group consisting of hydrogen, alkyl having from 1 to 6 carbon atoms, a radical having the formula ROH wherein R has the above-stated meaning, a fluorinated acyl radical having the formula wherein R; has the above-stated meaning and a radical having the formula o,H2,-N-Y wherein x and Y have the above-stated meanings, with the proviso that at least one of Y or Y is a fluorinated acyl radical or one of Y is a radical having the formula C,H2;NY
in which x is as stated above and Y is a fluorinated acyl radical, said fluorinated acyl radical having the aforestated formula, and at least one of Y or Y is hydrogen.
The fluorinated polyamide reactant of Formula II, above IS prepared by reaction of a fluorinated carboxylic acid having the formula R COOH wherein R, has the afore-stated meaning, or a derivative thereof, such as an ester, anhydride or acid halide thereof with a polyalkylene polyamine compound corresponding to the general formu a NH: o xHarl n yC xHaNHQ wherein x and y have the afore-stated meanings; wherein Q is selected from the group consisting of hydrogen, alkyl having from 1 to 6 carbon atoms, and a radical having the formula ROH wherein R has the afore-stated meanmg; and wherein Q is selected from the group consisting of hydrogen, alkyl having from 1 to 6 carbon atoms, a radical having the formula ROH wherein R has the afore-stated meaning, or an aminoalkyl radical having the formula C H NHQ wherein x and Q have the afore-stated meanings; there being at least two hydrogen atoms in the molecule represented by Q and/or Q.
The polyalkylene polyamine reactants of Formula III, above, employed in the preparation of the fluorinated polyamide compounds of Formula II, above, as a class,
are known compounds. These reactants may be straightchain or branched-chain compounds and may be used in the form of a single compound, as a mixture of isomers or as a mixture of polyamines containing from 3 to 6 nitrogen atoms in the molecule. Specific examples of polyalkylene polyamines employable herein include diethylene triamine, di r1 propylene triamine, di-butylene triamine, di-n-hexylene triamine, triethylene tetramine, tri-i-propylene tetramine, tri n hexylene tetramine, 4- (2 aminoethyl) 1,4,7 triazaheptane, tetraethylene pentamine, tetra n propylene pentamine, tetra-n-butylene pentamine, 4 (2 aminoethyl) 1,4,7,l tetraazadecane, tetra n hexylene pentamine, pentaethylene hexamine, 1 (hydroxyethyl) 1,4,7 triazaheptane, 1- methyl 8 (6 heydroxyhexyl) l,4,8,12 tetraazadodecane, 1-(6-hydroxyhexyl)l1,16-dimethyl 1,11,16,21- tetraazaheneicosane, 1,7 bis(2 hydroxyethyl) 1,4,7, 10 tetraazadecane, 4 methyl 1,4,7,10 tetraazadecane, and l-methyl 1,5,9 triazanonane. These polyalkylene polyamines can be prepared by standard methods known to those skilled in the art. Preferred polyalkylene polyamines are diethylene triamine, dipropylene triamine,
triethylene tetramine and tetraethylene pentamine since these are the more readily commercially available compounds.
Fluorinated carboxylic acid reactants, above described, wherein R is perfluoroalkyl, suitable for reaction with the above polyalkylene polyamine reactants are saturated straight-chain or branched-chain monocarboxylic acids or stated derivatives thereof containing from 4 to 18 carbon atoms in the acid portion of the molecule. Discrete molecular species of the perfluorocarboxylic acid reactants may be used or mixtures of these reactants in various proportions having the indicated carbon chain length may be employed. Illustrative perfiuorocarboxylic acid reactants include perfluorobutyric, perfiuorocaproic, perfluorocaprylic, perfluorolauric, perfluoromyristic, perfluoropalmitic, and perfluorostearic acids, as well as various isomeric forms thereof.
Perfluorocarboxylic acid reactants herein contemplated containing up to about ten carbon atoms are readily prepared by the electrochemical fluoroination of alkanoic acids in anhydrous hydrogen fluoride with subsequent hydrolysis of the resulting fluorinated acid fluorides, as disclosed in US. Pat. 2,567,011, issued Sept. 4, 1951. Longer chain perfluorocarboxylic acid reactants, i.e. those containing from about 11 to 18 carbon atoms, may be obtained by reaction of perfluoroalkyl iodides with oleum containing about 15% to 45% sulfur trioxide at elevated temperatures followed by hydrolysis of the resulting perfluorocarboxylic acid fluoride, as disclosed in French Pat. 1,343,601 of Oct. 14, 1963.
Fluorinated carboxylic acid reactants, above described, wherein R, is a radical having the formula wherein R R X, r, n, m and p have the afore-stated meanings may be prepared by various hereinafter described methods.
Fluorinated carboxylic acids of the formula R COOH wherein R; has the Formula IV, above, wherein m is at least 1 and the sum of n and p is at least 1, can be prepared from telomers having the general formula wherein R and R have the afore-stated meanings, wherein s and t are each integers from 0 to 20, the sum of s and I being at least 1, and wherein E is a halogen selected from the group consisting of Br and I. Telomers of that type and their preparation are described in commonly assigned copending application of Anello et al. entitled, Telomers and Process for the Preparation Thereof, Ser. No. 633,359, filed Apr. 25, 1967 now U.S. Pat. 3,514,487, the pertinent subject matter of which is hereby incorporated by reference. By way of general description, these telomers are prepared by radical addition reactions of polyfluoroisoalkoxyalkyl halide telogens of the formula wherein R R and E have the afore-stated meanings, with telomerizable unsaturated compounds. The telomerization reaction may be initiated by heat or by means of a free radical initiating catalyst. The polyfluoroisoalkoxyalkyl halide telogen starting materials may be prepared by reacting a corresponding halogenated ketone with an ionizable flouride salt, e.g. C F, to form a fluorinated organic salt and then reacting the organic salt with a halogen other than fluorine and an olefin. Preparation of the telogen starting materials is described in detail in copending applications of Litt et al., Fluorinated Ethers, U.S. Ser. Nos. 492,276 and 513,574, filed Oct. 1, 1965, and Dec. 13, 1965, respectively now US. Pats. 3,453,333 and 3,470,256 respectively, the pertinent subject matter of which applications is hereby incorporated by reference.
Fluorinated carboxylic acids of the formula R COO'H wherein R has the Formula IV, above, wherein r, n and p are all 0 and wherein m is at least 2 may be prepared by reacting the corresponding telomer represented by general Formula V, above, wherein t is 0 with ICN or (CN) to form the nitrile, followed by hydrolysis of the nitrile in known manner to form the free acid. The reaction between the telomer and the ICN or (CN) to form the nitrile is carried out under superatmospheric pressure above about 20 to 200 atmospheres or more at temperatures in excess of about 300 C., preferably using an excess of the ICN or (CN) reactant. Hydrolysis of the nitrile to form the free acid can be effected by treatment with aqueous mineral acid, such as hydrochloric, phosphoric, or sulfuric acid, at temperatures between about 60 and about 125 C.
Fluorinated carboxylic acids of the formula R COOI-I wherein R has the Formula IV, above, wherein m is at least 1, p and r are both 0 and n is greater than 0 may be prepared by reacting the corresponding telomer represented by Formula V, above, wherein t is greater than 0 with an alkali metal cyanide to form the nitrile, followed by hydrolysis of the nitrile to form the free acid, as described above. The reaction between the telomer and the alkali metal cyanide is preferably carried out in aqueous alcoholic solution at temperatures between about 60 and about C.
Fluorinated carboxylic acids of the formula R COOH wherein R has the Formula IV, above, wherein m is at least 1, r is O, p is l and X is hydrogen can be prepared by reacting the corresponding telomer represented by general Formula V, above, wherein t is at least 1 with S0 to form the corresponding pyrosulfate, or with oleum to form the corresponding hydrosulfate, hydrolysis of the pyrosulfate or the hydrosulfate with aqueous acid to form the corresponding alcohol, followed by oxidation of the alcohol with dichromate, permanganate or strong nitric acid to form the free acid.
Fluorinated carboxylic acids of the formula R COOH wherein R, has the Formula IV, above, where m is at least 1, r and n are both 0, p is 1 and X is fluorine can be prepared by reacting a corresponding telomer represented by Formula V, above, wherein t is with $0 to form corresponding acid halides and halopyrosulfates, and hydrolyzing the acid halides and halopyrosulfates by refluxing with water to obtain the corresponding free acids. Fluorinated carboxylic acids of the formula R COOH wherein R: has the Formula IV, above, wherein r is 1 and m, n and p are all 0 can be prepared by the same method from polyfluoroisoalkoxyalkyl halide compounds of Formula VI, above.
Fluorinated carboxylic acids of the formula R COOH wherein R; has the Formula IV, above, wherein mis 1 and r, n and p are all 0 can be prepared from polyfluoroisoalkoxyalkyl halide compounds of Formula VI, above, by reacting them with a Grignard reagent to form a magnesium halide adduct, reacting this adduct with CO to form a magnesium halide salt, and then acidifying the salt to obtain the desired acid. The reactions involving the Grignard reagent and the carbon dioxide proceed very rapidly and can be conducted at tempera tures considerably below 0 C. Preparation of these acids is described in detail in commonly assigned co-pending application of Litt et al., Fluorinated Ethers, U.S. Ser. No. 492,276, filed Oct. 1, 1965, now U.S. Pat. 3,453,- 333, referred to above.
The esters and acid halides of the above-described acids may be prepared from the acids by conventional procedures.
While the telomers of Formula V, above, and the fluorinated carboxylic acid reactants derived therefrom, may be prepared as discrete compounds, they are generally obtained as mixtures of compounds of varying chain length. It is to be understood that both, the individual discrete fluorinated carboxylic acid reactants as well as their mixtures of compounds of varying chain length are suitable for the preparation of the fluorinated polyamide compounds employed in the preparation of the compounds of the present invention.
Preparation of the above-described acids wherein R, has the Formula IV, above, is described in more detail in commonly assigned copending applications of Anello et al., U.S. Ser. Nos. 721,115 and 721,117, both filed Apr. 12, 1968, respectively entitled Fluorocarbon Acids and Derivatives and Fluorocarbon Compounds, the pertinent subject matter of which application is hereby incorporated by reference.
The fluorinated polyamide reactants of Formula II, above, may be prepared by simply mixing the fluorinated carboxylic acid reactant with the polyalkylene polyamine Starting material of Formula III, above. These reactants may be charged in a molar proportion of 1 mol of polyalkylene polyamine to about 1 to 7 mols of fluorinated carboxylic acid reactant. If desired, the reaction may be carried out in the presence of a suitable inert organic solvent. Suitable reaction temperatures range between about 0 C. to about 200 C. Upon conclusion of the reaction, the desired fluorinated polyamide compound may be recovered from the reaction mixture by methods known to those skilled in the art.
The reaction product, obtained as a result of the reaction of the fluorinated carboxylic acid reactant and the polyalkylene polyamine reactant above described, may comprise a single compound conforming to the above stated structural Formula II, a mixture of isomers thereof or a reaction mass composed of amide products containing two or more amide functions depending upon the polyalkylene polyamine reactant employed, the reactivity of the fluorinated carboxylic acid reactant present, the solubility of the amide product obtained during the reaction in the reaction mixture and the molar proportions of fluorinated carboxylic acid reactant employed. The resulting fluorinated polyamide product whether it comprises a single compound, a mixture of isomers thereof or a mass composed of amide products containing tWo or more amide functions, is suitable without further purification for reaction with the wunsaturated acyl halide reactant, above described, to form the fluorocarbon derivatives of the present invention. However, if desired, the fluorinated polyamide may be further purified prior to reaction with the tar-unsaturated acyl halide reactant, as by distillation or recrystallization using any commonly employed inert organic solvent such as acetonitrile or chloroform.
DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel fluorocarbon derivatives of this invention are prepared by reacting the a-unsaturated acyl halide reactant with the fluorinated polyamide starting material, above described. These reactants may be charged in a mol proportion of 1 mol of fluorinated polyamide to about 1 to 10, preferably about 2 to 4, mols of tat-unsaturated acyl halide reactant. Reaction temperature and time are dependent upon the particular fluorinated polyamide and zit-unsaturated acyl halide reactants involved. The temperature ranges from about 0 C. to about 160 C., preferably about 10 C. to about C. The reaction is quite rapid even at about room temperature. Reaction times generally range between about 10 minutes and about 4 hours. If desired, the reaction may be conducted in the presence of an inert organic solvent and, when present, the maximum temperature employable is limited only by the reflux temperature of the reaction mixture. Although the reaction may be carried out under superatmospheric pressure, it is preferred to conduct the reaction at atmospheric pressure.
The reaction of the fluorinated polyamide starting material with the tat-unsaturated acyl halide reactant yields as by-product the halide salt of the polyamide starting material, as illustrated by the equation below which shows the reaction of 1,7-bis(perfluorooctanoyl)-1,4,7- triazaheptane with acrylyl chloride:
Upon completion of the reaction the desired product can be extracted from the reaction mixture using a suitable solvent, such as ether, acetone, acetonitrile, and the like, and can be purified, as e.g. by fractional crystallization. In a preferred embodiment the reaction is carried out in an acetone medium. Acetone dissolves the starting ma terials and the desired product, but not the by-product halide salt. Thus, recovery of the desired product is facilitated in that, upon completion of the reaction, the reaction, the by-product halide salt can be simply removed by filtration of the reaction mixture. The halide salt by-product can be reconverted to the fluorinated polyamide starting material in known manner by treatment with an appropriate ion exchange resin or with an aqueous base, such as aqueous sodium hydroxide.
To prevent polymerization of the tat-unsaturated acyl halide reactant during the reaction, it is preferred to conduct the reaction in the presence of one of the Well known free radical inhibitors, such as u-pinene. The free radical inhibitor, if one is used, is employed in amount of between 0.01% to about 1.0% by weight, based on the total Weight of the reaction mixture.
The reaction is preferably carried out in the presence of an acid-interceptor, such as sodium bicarbonate, to thereby increase the yield of the desired product and to reduce the amount of by-product halide salt formed in the reaction.
Since the tit-unsaturated acyl halide reactant is decomposed by Water, the reaction is preferably carried out under exclusion of water using anhydrous reagents.
The alkylene linkage (C H in the novel compounds of the present invention may be a straight-chain or branched-chain group, preferably containing from 2 to 4 carbon atoms.
The R groups in the novel fluorocarbon derivatives of the present invention represented by Formula I, above, may be the same or different. When the R; group is a perfluoroalkyl group, it may be straight-chain or branchedchain, preferably containing from 6 to 14 carbon atoms.
When the R; group is a fluorinated isoalkoxyalkyl group represented by Formula IV, above, then, in the moiety, R and R are preferably fluorine or perfluoroalkyl groups. When perfluoroalkyl groups, R, and R preferably contain 1-2 carbon atoms. When the R and R groups contain hydrogen substitution, the atomic ratio of fluorine to hydrogen is at least 1: 1.
In preferred embodiments integer m in the Rf radical of Formula IV, above, is at least 1, and the sum of m and n is preferably from 1 to 10. Specific examples of preferred embodiments of the preferred moiety of the R radical of the compounds of the present invention include the following:
(VII) wherein R R R R and y have the aforestated mean ings and x is an integer from 2 to 4 constitute preferred embodiments of the present invention, those wherein R is selected from the group consisting of H and methyl, and wherein R and R are independently selected from the group consisting of H and alkyl having from 1 to 2 carbon atoms being more preferred yet. Acrylyl and methacrylyl 10 radicals are specific examples of preferred tit-unsaturated acyl radicals.
A specific class of preferred embodiments of the present invention are compounds according to Formula VII, above, wherein the R; radical has the formula wherein m is an integer from 1 to 10, n is an integer from 0 to 10, with the proviso that the sum of m and n is from 1 to 10, and wherein X and p have the aforestated meanings.
The following examples relate to the preparation of representative compounds of the present invention but are not intended to be limiting on the scope thereof.
EXAMPLE 1 Sodium bicarbonate (17.8 g., 0.21 mol) and ten drops of a-pinene are added to a stirred solution of 1,7-bis(perfluorooctanoyl)-l,4,7-triazaheptane (53 g., 0.06 mol) in 500 ml. of acetone at 10 C. To this mixture is added under constant stirring a total 9.0 g. (0.1 mol) of acrylyl chloride, and stirring at 1015 C. is continued for three hours. After that time the reaction mixture is filtered to remove insoluble material, and the clear filtrate is evaporated to dryness to yield about 30 g. of crude product. The crude product is twice recrystallized from acetonitrile to yield about 20 g. of the colorless solid product, 1,7-bis- (perfluorooctanoyl)-4-acrylyl-2,4,7 triazaheptane, having the formula A portion of that product is subjected to further recrystallization from acetonitrile to yield an analytical sample (M.P. 115116 0.).
Analysis.Calcd. for C H O N F (percent): C, 29.1; H, 1.39; N, 4.42; F, 60.0. Found (percent): C, 29.4; H, 1.14; N, 4.78; F, 59.26.
Assigned structure is confirmed by infrared spectrographic analysis.
The 1,7-bis (perfluorooctanoyl) -1,4,7-triazaheptane reactant is prepared in the following manner:
A solution of 49 grams (0.475 mol) of diethylene triamine in 60 ml. of diethyl ether is placed in a reaction vessel equipped with a dropping funnel, condenser, magnetic stirrer and a calcium chloride drying tube. After chilling the vessel in an ice water bath for a period of about 20 minutes, 34.2 grams (0.079 mol) of n-perfluorooctanoyl chloride is added with stirring to the contents of the vessel during a 30 minute period. After addition of the n-perfluorooctanoyl chloride reactant is complete, the ice water bath is removed and the stirring is continued at room temperature for a period of 20 minutes. Thereafter ml. of an 8% aqueous sodium hydroxide solution is added to the reaction mixture and the stirring is continued for an additional 15 minutes. The resulting gelatinous precipitate is filtered at reduced pressure and Washed with water. After air drying the precipitate, a yield of about 30 grams of 1,7-di-n-perfluoro0ctanoyl-1,4,7-triazaheptane, a white solid (melting point 9497 C.), having the following structural formula is obtained:
EXAMPLE 2 Following the procedure of Example 1 there is reacted 1,9-di-n-perfluorooctanoyl-1,5,9-triazaheptane with methacrylyl fluoride to obtain as product the compound The 1,9-di-n-perfluorooctanoyl-1,5,9-triazaheptane reactant is prepared in the following manner:
To a solution of 20 grams (0.0467 mol) of methyl-m perfluorooctanoate in 25 ml. of diethyl ether, there is added 3.07 grams (0.0235 mol) of di-n-propylene triamine. The resulting solution is heated under reflux temperature for a period of 24 hours. After removal of the solvent under reduced pressure, 16.6 grams of a light yellow oil which solidifies in about 30 minutes to give a white sticky solid is obtained. The white sticky solid is recrystallized from acetonitrile to yield 1,9-di-n-perfluorooctanoyl-1,5,9- triazanonane (a white powder melting at 84-85 C.) having the following structural formula:
EXAMPLE 3 Following the procedure set forth in Example 1 there is reacted the amide with methacrylyl chloride to obtain as product the compound The amide reactant is prepared in the following manner: To a solution of 24.7 g. (0.05 mol) of in 25 ml. of diethyl ether there is added 3.07 g. (0.0235 mol) of di-n-propylene triamine. The resulting solution is heated under reflux for a period of 24 hours. After removal of the solvent under reduced pressure there is obtained the crude product (CF CFO (CF CONHCH CH CH NH which can be purified by recrystallization from acetonitrile.
EXAMPLE 4 Following the procedure set forth in Example 1 there is reacted l,lO-di-n-perfluorooctanoyl-1,4,7,lO-tetraazadecane with acrylyl bromide to obtain as product the compound The 1, IO-di-n-perfluorooctanoyl-1,4,7, lO-tetraflzadecane reactant is prepared in the following manner:
To a solution of 20 grams (0.0467 mol) of methyl-nperfluorooctanoate in 25 ml. of diethyl ether, there is added 3.4 grams (0.0233 mol) of triethylene tetrarnine. The resulting solution is heated under reflux temperature for a period of 24 hours. After removal of the solvent under reduced pressure, 20 grams of a white solid is obtained which is subsequently recrystallized from acetonitrile. The product of this reaction is 1,10-di-n-perfiuorooctanoyl-1,4,7-tetraazadecane, a white powder (melting point 89-92 C.) having the following structural formula:
OH H H HO EXAMPLE 5 To a solution of 16 grams (0.037 mol) of methyl perfiuorooctanoate in 20 of diethyl ether there is added 3.5 grams (0.018 mol) of tetraethylenepentamine. The resulting solution is heated to reflux temperature for a period of 3 hours. After removal of the diethyl ether solvent under reduced pressure there remains a viscous yellow oil which does not solidify on standing. This oil is dissolved in 250 ml. of acetone, 16.0 g. (0.19 mol) of sodium bicarbonate and 5 drops of a-pinene are added, the solution is stirred, and 9.4 g. (0.09 mol) of methacrylyl In manner analogous to that described in the above examples, other compounds illustrative of the present invention may be prepared as follows:
iodide.
CF3 Fa O 0E3 CF F- -cFlor(orm-(i-Nnczmtvclmib-ii-tormcForge-F CFs C4119 3 s by reaction of 1,7-di-[(4,6-di-trifluoromethyl) perfluoroheptanoyl]-l,4,7-triazaheptane with 2-ethyl-3-butyl-3- by reaction of 1,7-di-n-perfluorotetradecanoyl-l,4,7-triaza heptane with 3-ethyl-3-hexylacrylyl bromide.
by reaction of 1,7-di-n-perfluorohexadecanoyl-1,4,7-triazaheptane with 2,3-dihexylacrylyl chloride.
ll 0 CH3 GsHis by reaction of l,lO-di-n-perfluorononanoyl-l,4,7,10-tetraazadecane with 3-hexylmethacrylyl fluoride.
by reaction of 1,l0-di-[(3,5,7-tris-trifluoromethyl) perfiuorononanoyl]-1,4,7,l0-tetraazadecane with 3 -butyl acrylyl chloride.
15 by reaction of 1,10 n-diperfluorooctanoyl-4-(2-aminoeth yl)-l,4,7,10-tetraazadecane with 3-amylmethacrylyl chloride.
by reaction of 1,l--di-n-perfluorooctanoyl-4-(Z-n-perfluorooctanamidoethyl)-1,4,7,l0-tetraazadecane with acrylyl chloride.
by reaction of 1,10-n-diperfluorooctanoyl-4-(2-aminoethyl)-l,4,7,lO-tetraazadecane with acrylyl chloride.
The oiland water-repellent compounds of the invention are useful in treating paper as Well as textiles (fabrics and fibers) comprised of natural or synthetic fibers including cotton, nylon, wool, polyethylene terephthalate and polyacrylonitrile. The fluorocarbon derivatives of the invention are especially useful in the treatment of fabrics and fibers comprised of cellulosic and certain cellulosic derivatives which contain cellulosic hydroxyl groups such as cotton, linen, viscose, cupra ammonium rayon, saponified cellulose acetate and salts of cellulose xanthate. The invention is also applicable to the treatment of blends of natural and/or synthetic fibers in cloth, for example, blends containing polyethylene terephthalate, polyacrylonitrile, nylon, cotton and wool. If desired, auxiliary agents such as those imparting water repellency, crease resistance and softening properties may be applied in conjunction with the fluorocarbon chemicals of the invention. In addition, other materials such as the surfaces of wood, plastics, glass and metals may be treated with solutions or suspensions containing the fluorocarbon derivatives of the invention to render the same oiland water-repellent.
The fluorocarbon derivatives of the present invention may be applied to the article to be rendered oiland water-repellent by treating the same with a solution of the repellent and evaporating the solvent. If desired, the treated article may then be cured at an elevated temperature. The concentration of the fluorocarbon derivative on the treated article generally may vary from about 0.5% to preferably 1.0% to 4.0%, based on the weight of the article. Since the solvent used in formulating the oiland Water-repellent composition functions essentially as a carrier for the fluorocarbon derivative, any organic liquid inert to the article to be treated and capable of dissolution of the requisite amount of oiland Water-repellency agent may be employed. Acetone, methyl ethyl ketone, acetonitrile and dimethylformamide are illustrative solvents which may be used in preparing the oiland water-repellent compositions. Alternatively, aqueous emulsions of the oiland water-repellent may be applied onto the articles to be treated by conventional aqueous application methods.
The solvent may be evaporated by air drying at room temperature. If it is desired to cure the treated articles the solvent may be evaporated prior to curing or during curing of the oiland water-repellent chemical onto the article. Preferably, the article treated with a solution of the fluorocarbon derivative is air dried prior to curing for a time suflicient to evaporate essentially all of the solvent. Thereafter, the article having on its surface the oiland water-repellent chemical is cured or heat-set at a temperature of about 100 C. to 160 C. for a time period varying inversely with the temperature, ranging from about 1 second to 5 minutes.
When cellulosic materials are to be rendered oiland Water-repellent, the fluorocarbon derivatives of the present invention are preferably applied thereto from an aqueous solution or an aqueous emulsion and in the presence of a catalyst of the type commonly used as crosslinking catalyst for crosslinking resins with cellulosic materials. The fluorocarbon derivatives of the present invention respond equally Well to basic as well as acidic catalysts, thus, have the decided advantage that their use is compatible with permanent press treatment, which treatment commonly employs acidic reactants. The cellulosic material is moistened with an aqueous solution of the catalyst, air dried to remove residual Water and then impregnated with an aqueous solution or emulsion of the fluorocarbon derivative of the invention for a time, normally 30 seconds to about 30 minutes, sufficient to retain on the cellulosic material about 1 to 10%, preferably 2 to 4% of the fluorocarbon derivative, based on the weight of the cellulosic material. The thusly impregnated cellulosic material is then heated at a temperature of C. to C. for a time period varying inversely with the temperature ranging from about 15 minutes to 30 seconds. After the reaction of the fluorocarbon derivative with the cellulosic material is complete, the chemically modified cellulosic material is Washed free of excess catalyst with water and dried.
Various modifications of the above-described treatment may also be employed without departing from the spirit of the invention. For example, the cellulosic material may be first impregnated with an aqueous solution or emulsion of the fluorocarbon derivative, then treated with an aqueous solution of the catalyst, air dried and finally heated to effect reaction of the fluorocarbon derivative With the cellulosic material. Another modification of the above-described procedure involves premixing the aqueous solution or emulsion of the fluorocarbon derivative together With the catalyst prior to impregnation of the cellulosic material. Chemical modification of the cellulosic material under anhydrous conditions, as in the presence of solvents capable of penetrating cellulosic fibers such as benzene, chloroform, dioxane and acetone, constitutes still another variation of the afore-described procedures.
In general, suitable basic catalysts should have a dis association constant in water of at least 1.8)(10 at 25 C. Phosphates, carbonates and hydroxides of alkali metals such as sodium phosphate, sodium carbonate, sodium hydroxide and potassium hydroxide; alkaline-earth metal hydroxides including calcium hydroxide and magnesium hydroxide; and quaternary ammonium hydroxides such as tetraethyl ammonium hydroxide and benzyl trimethyl ammonium hydroxide are illustrative of preferred effective basic catalysts. Suitable acid catalysts are the mineral acids and strong organic acids, as well as the ammonium salts, amine salts and metal salts of strong acids. The salts of strong acids are preferred acid catalysts, ammonium chloride, magnesium chloride, zinc nitrate and zinc chloride being specific examples of preferred acid catalysts. The catalyst concentration is normally dependent upon the strength of the acid or base catalyst selected, speed of reaction desired and the nature of the cellulosic material to be treated. In general, catalyst concentrations of about 1 to 20%, preferably 2 to 5%, based on the Weight of the solution are satisfactory.
Results of tests relating to the evaluation of a typical fluorocarbon derivative composition of the present invention as oiland water-repellency agent on textiles are shown below.
The procedure employed in determining the oil-repellency ratings on textiles is described, for example, on pages 323-4 of the April 1962 edition of the Textile Research Journal. This procedure involves gently placing on the treated fabric drops of mixtures of mineral TABLE I Oll-repelleney Percent Percent rating mineral oil a n-heptane b 10 No holdout to mineral oil Nujol Saybolt viscosity 360/390 at F. Specific gravity 0.880/0.900 at 60 F. Percent by volume at 20 C.
b IEEegtane B.P. 9899C. Percent by volume When typical oily staining materials are dropped onto treated fabrics and subsequently blotted 01f, those fabrics with an oil-repellency rating of 50-70 will exhibit only fair resistance to staining; those fabrics with an oil-repellency rating of 80-90 will have good resistance to staining; and those with an oil-repellency rating of 100 and up will give excellent resistance.
Wash fastness of the treated cloth was determined by subjecting the cloth to repeated launderings in hot wat r in a household automatic washing machine using a heavy duty detergent, followed by drying in an automatic drier. The material was ironed prior to testing.
The results obtained are set forth in Table II below:
(b) Same as in (a) above, except that prior to impregnation with the acetone solution of the fluorocarbon compound the test pieces were totally immersed in a 5% aqueous magnesium chloride solution, were wrung out, and were then dried at 80 C. for 8 minutes.
(0) Same as in (a) above, except that prior to impregnation with the acetone solution of the fluorocarbon cornpound the test pieces were totally immersed in a 5% aqueous sodium hydroxide solution, were wrung out, and were then dried at 80 C. for 8 minutes.
When water was placed on test pieces impregnated as shown above, the water did not penetrate the fabric, but formed beads on the surface thereof which could be removed as by shaking the fabric. Thus, the fabric so treated had oilas well as water-repellent properties.
The result of a test relating to the evaluation of a typical fluorocarbon derivative of the present invention as oil-repellency agent on paper is shown below.
The procedure employed in deterimining the oil-repellency ratings on paper is described, for example, in a Technical Bulletin issued by the Minnesota Mining and Manufacturing Company, entitled Paper Chemical FC- 805-IV. Properties of Treated Paper-C. Oil Resistance- 2. Comparative Kit Test. This procedure involves gently placing on treated paper drops of mixtures of castor oil, toluene and heptane in varying proportions. The drops are allowed to stand on the treated paper undisturbed for 15 seconds. After the 15 second period the wetting and penetration of the paper is visually observed. Failure is detected by pronounced darkening caused by penetration. The darkening of even a small fraction of the area under the drop is considered failure. Referring to following Table III, the number corresponding to the mixture containing the highest percentage of heptane which does not penetrate or wet the paper is the Kit Number of the paper and is considered to be the oil-repellency rating of the treated paper.
TABLE II Oil repellency alter launderings Speci- Substrate men 0 l 2 3 4 5 6 Cotton print cloth a 150 120 80 60 80 60 Spun nylon cloth a 110 70 Type 54 Dacron/cotton blend cloth-.." a 140 120. 110 110 100 100 The test specimens, pieces of 80 x 80 count white cot- TABLE III ton print cloth, spun 100% Nylon cloth, Type 54 Dacron (T.M.)/cotton blend poplin weight cloth, were treated oasto r oil, Tollllene, Heptane, with a 1.75 percent solution of 1,7-bis (perfluorooctanoyl)- 65 ume Wlum" 4-acrylyl-1,4,7-triazaheptane in acetone as follows: 200 0 o (a) The test specimens were impregnated by total un- 1: "j: 180 10 10 mersion in the acetone solution of the fluorocarbon com- E3 g3 g8 pound for 3 minutes. The specimens were then dried at 120 40 40 80 C. for two minutes, and were then heated in an oven 70 lgg 2g 58 at C. for four minutes. Prior to initial test, the speci- 60 70 s mens were washed in warm water, dried at 80 C. for 10 g3 3g 88 minutes, ironed, and conditioned at 50% RH. After each 0 100 3 laundering the test pieces were likewise subjected to iron- 0 90 110 ing and conditioning of 50% RH. 75
Papers having a Kit Number of about 5-6 or below will exhibit only fair oil-repellency; those papers having 8. Kit Number of about 8-10 will have good oil-repellency, and those having a Kit Number of about 10 and up will have excellent oil-repellency.
Unsized paper hand sheets of 50/50 hardwood/softwood kraft pulp beaten to 400 ml. Canadian Standard freeness were impregnated by total immersion for 1 minute in about 0.4 percent by weight solution of 1,7-bis (per fluorooctanoyl)-4-acrylyl-1,4,7-triazaheptane in acetone. Excess solution was blotted from the hand sheets. The hand sheets were then dried at 230 F. for approximately one minute and were then tested for oil resistance by the above-described Kit Test. The Kit Numbers of the paper so treated Were 10-11, indicating excellent oil-repellency.
When other fluorocarbon compounds Within the scope of the present invention are applied to textiles and paper in the above-described manner similar results are obtained, that is to say good oiland water-repellency is imparted to the textiles and paper so treated.
From the foregoing it is apparent that we have discovered a series of novel and valuable compounds which are oiland water-repellent agents which also provide maintenance of oleophobic and hydrophobic properties of substrate surfaces treated therewith after their repeated exposure to laundering treatments.
Since various changes and modifications may be made in the invention without departing from the spirit there of, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
We claim:
1. Compounds having the structural formula II I I ll R[CN(C;H:;N) -C;H2x-'NCR1 TR R:- R
wherein (I) R; is a radical selected from the group consisting of (a) perfluoroalkyl having from to 15 carbon atoms, and
(b) a radical having the formula wherein (i) m and n are each integers of from 0 to 0 to 5, with the proviso that the sum of m and n is from 0 tell) and provided further that when r is O, m is at least 1,
(ii) X is selected from the group consisting of hydrogen and fluorine, with the proviso that when n is greater than 0, then X is always hydrogen,
(iii) p is 0 or 1,
(iv) r is 0 or 1, with the proviso that when the sum of m, n and p is greater than 0, then r is alw y 0;
(2) x is an integer from 2 to 3,
(3) y is an integer from 1 to 3,
(4) R R and R are independently selected from the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms.
2. Compounds according to claim 1 wherein R is a perfluoroalkyl radical having from 6 to 14 carbon atoms.
3. Compounds according to claim 2 wherein R" is selected from the group consisting of hydrogen and methyl, and wherein R and R are independently selected from the group consisting of hydrogen and alkyl having from 1 to 2 carbon atoms.
4. Compounds according to claim 3 wherein R and R are both H.
5. A compound according to claim 4 having the structural formula 6'. A compound according to claim 4 having the structural formula 7. A compound according to claim 4 having the structural formula 8. A compound according to claim 4 having the structural formula 9. Compounds according to claim 1 wherein R, is a radical having the formula wherein m, n, r, p and X have the meanings given in claim 1.
10. Compounds according to claim 9 wherein R is selected from the group consisting of hydrogen and methyl and wherein R and R are independently selected from the group consisting of hydrogen and alkyl having from 1 to 2 carbon atoms.
11, Compounds according to claim 10 wherein R and R are both hydrogen.
12. A compound aCcOrding to claim 11 having the structural formula [(CF CFO(CF CONHC H N COCH=CH 13. A compound according to claim 11 having the structural formula COCH=CH 22 References Cited UNITED STATES PATENTS 2,528,274 10/ 1950 Gunderson 2604O4.5 2,593,737 4/1952 Diesslin et a1 260- 514 3,038,820 6/ 1962 Albrecht 260404.5 3,185,539 5/1965 Madison et al. 260 561 3,420,697 1/ 1969 Sweeney et a1. .4 260404.5 3,428,709 2/1969 Kleiner 260404.5 3,446,570 5/1969 Sweeney et al. 260404.5 3,453,333 7/1969 Litt et a1. 260633 3,458,571 7/1969 Tokoli 260404.5 3,470,256 9/1969 Evans et a1. 260611 FOREIGN PATENTS 1,111,396 4/1968 Great Britain 260404.5
LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner US. Cl. X.R.
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US20080039605A1 (en) * 2006-08-08 2008-02-14 Weiming Qiu Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
WO2008021153A3 (en) * 2006-08-08 2008-05-02 Du Pont Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
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US7754838B2 (en) 2006-08-08 2010-07-13 E.I. Du Pont De Nemours And Company Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
US20100233419A1 (en) * 2006-08-08 2010-09-16 E.I.Du Pont De Nemours And Company Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
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EP2287270A2 (en) 2006-08-08 2011-02-23 E. I. du Pont de Nemours and Company Composition containing fluorinated amide
US8178638B2 (en) * 2006-08-08 2012-05-15 E.I. Du Pont De Nemours And Company Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
US20120264972A1 (en) * 2006-08-08 2012-10-18 E. I. Du Pont De Nemours And Company Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
US8389657B2 (en) * 2006-08-08 2013-03-05 E. I. Du Pont De Nemours And Company Poly(meth)acrylamides and poly(meth)acrylates containing flourinated amide
CN106905197A (en) * 2017-03-08 2017-06-30 江苏理文化工有限公司 A kind of fluorine-containing propene acid amides and its synthetic method

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