US3576017A - Haloalkanoyl derivatives of fluorinated amides - Google Patents

Haloalkanoyl derivatives of fluorinated amides Download PDF

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US3576017A
US3576017A US749321A US3576017DA US3576017A US 3576017 A US3576017 A US 3576017A US 749321 A US749321 A US 749321A US 3576017D A US3576017D A US 3576017DA US 3576017 A US3576017 A US 3576017A
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formula
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fluorinated
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haloalkanoyl
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Richard F Sweeney
Alson K Price
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Honeywell International Inc
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Allied Chemical 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

  • Haloalkanoyl 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, hydroxyalkyl, a fluorinated acyl radical R CO- wherein R, is as described above, or a haloalkanoyl radical; and Z is H, alkyl, hydroxyalkyl, a fluorinated acyl radical R,CO wherein R; is as described above, a haloalkanoyl radical or a radical having the formula CXH2XNHZ wherein Z is as described above, there being at least one fluorinated acyl radical R CO- and at least one haloalkanoyl radical in the molecule represented by Z and/
  • This invention is directed to a new class of fluorcarbon 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 haloalkanoyl halides, 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 textiles, paper and other fibrous products to impart thereto oiland water-repellency properties.
  • these fluorochemicals are composed of a fluorinated alkyl chain affixed to an active functional group.
  • the oleophobic and hydrophobic properties of the fluorochemicals 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 afiixed 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.
  • 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.
  • 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 materials, 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 haloalkanoyl halides have been found to impart to textiles, paper and other fibrous products durable oiland water-repellency properties.
  • R is a radical selected from the group consisting of (a) perfluoroalkyl having from 3 to 17 carbon atoms,
  • 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,
  • n 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,
  • 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 hy drogen,
  • (v) r is 0 or 1, with the proviso that when the sum of m, n and p is greater than 0, and r is always 0,
  • novel fluorocarbon derivatives of the present invention may be prepared by reacting a fiuorinated polyamide starting material as hereiubelow defined with a haloalkanoyl halide reactant at temperatures between about 0 C. and about 100 C., preferably in the presence of an inert organic solvent.
  • haloalkanoyl halide reactant employed in the preparation of the novel fluorocarbon derivatives of the preseut invention is represented by the formula wherein X is a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, and Y is a haloalkyl radical, straight chain or branched chain, having from 1 to 6 carbon atoms and containing from 1 to 2 halogen atoms independently selected from the group consisting of chlorine and bromine, which halogen atoms may be arranged on the carbon chain in any available position.
  • haloalkanoyl halide reactants herein contemplated, as a class are known compounds which can be prepared by conventional methods known to those skilled in the art.
  • a partial listing of readily available haloalkanoyl halides, or of haloalkanoyl halides based on readily available halogenated aliphatic carboxylic acids, suitable for making compounds of the present invention includes bromoacetyl bromide, chloroacetyl chloride, tat-bromopropionyl bromide, dichloroacetyl chloride, oc-ChlOI'OPI'OPlOIlYl chloride, fl-chloropropionyl chloride, a-bromo-iso-butyryl bromide, chloroacetyl iodide, bromoacetyl bromide, a-bromo-nbutyryl bromide, fltbIQlIlO-Il-Vfll
  • M 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 and a fiuorinated acyl radical having the formula wherein R, has the above-stated meaning; and M, which may be the same or different in different 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 0 H C'Rf wherein R, has the above-stated meaning, and a radical having the formula wherein x and M have the above-stated meanings, with the proviso that at least one of M
  • the fluorinated polyamide reactant of Formula II, above, is prepared by reaction of a fiuorinated carboxylic acid having the formula R COOfl 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 formula NH2( ;H2xl I )Y CXH2XNHQ, (III) wherein x and y have the afore-stated meanings; 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 meaning; and wherein Q is selected from the group consisting of hydrogen, alkyl having from i to 6 carbon atoms, a radical having the formula ROM wherein R has the aforestated meaning, or an aminoalkyl radical having the formula C H NQ wherein at and Q have the afor
  • 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 polyamides containing from 3 to 6 nitrogen atoms in the molecule.
  • polyalkylene polyamines employable herein include diethylene triamine, di-n-propylene triamine, di-i-butylene triamine, di-n-hexylene triamine, triethylene tetramine, tri-i-propylene tetramine, tri-n-hexylene tetramine, 4-(2- aminoethyl)-1,4,7-triazaheptane, tetra 11 hexylene pentamine, pentaethylene hexamine, 1-(hydroxyethyl)-1,4,7- triazaheptane, 1 methyl-8-(6-hydroxyhexyl)-1,4,8,12-tetraazadodecane, 1-(6-hydroxyhexyl) 11,16 dimethyl- 1,11,16,21 tetraazaheneicosane, l,7-bis(2-hydroxyethyl)- 1,4,7,10-tetraazadecane, 4-rnethyl-1,4,7,10-
  • polyalkylene polyamines can be prepared by standard methods known to those skilled in the art.
  • Preferred polyalkylene polyamines are diethylene triamine, dipropylene triamine, triethylene triamine 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 perfluorocarboxylic acid reactants include perfluorobutyric, perfluorocaproic, perfluoro-caprylic, 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 fluorination 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.
  • R and R have the afore-stated meanings, wherein s and t are each integers from 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 US. Pat. 3,514,487, the pertinent subject matter of which is hereby incorporated by reference.
  • these telomers are prepared by radical addition reactions of polyfiuoroisoalkoxyalkyl 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 fluorinated ketone with an ionizable fluoride salt, e.g. CsF, to form a fluorinated organic salt and then reacting the organic salt with a halogen other than fluorine or chlorine and an olefin.
  • Fluorinated carboxylic acids of the formula R COOH 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 C. and about 125 C.
  • Fluorinated carboxylic acids of the formula R COOH 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 100 C.
  • Fluorinated carboxylic acids of the formula R COOH wherein R has the Formula IV, above, wherein m is at least 1, r is 0, p is 1 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, wherein m is at least 1, n and r are both 0, p is 1 and X is fluorine can be prepared by reacting a corresponding telomer represented by Formula V, above, wherein Z is O with to form corresponding acid halides and fluoropyrosulfates and hydrolyzing the acid halides and fluoropyrosulfates 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 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 m is 1 and r, n and p are all 0 can be prepared from polyfluoroisoal-koxyalkyl 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 temperatures 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 fiuorinated carboxylic acid reactants as well as their mixtures of compounds of varying chain length are suitable for the preparation of the fiuorinated polyamide compounds employed in the preparation of the compounds of the present invention.
  • the fluorinated polyamide may be further purified prior to reaction with the haloalkanoyl 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 haloalkanoyl halide reactant with the fiuorinated polyamide starting material in a mol proporation of 1 mol of fiuorinated polyamide to about 0.5 to 10, preferably about 0.5 to 4, mols of haloalkanoyl halide.
  • Reaction temperature and time are dependent upon the particular fiuorinated polyamide and haloalkanoyl halide reactants involved. The temperature ranges from about 0 C. to about 100 C. preferably from about 10 C. to about 30 C. The reaction is quite rapid even at low temperatures. Reaction times generally range between about 10 minutes and about 4 hours.
  • the reaction may be conducted in the presence of an inert organic solvent.
  • the reaction may be carried out under super-atmospheric 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 crystallizatron.
  • a suitable solvent such as ether, acetone, acetonitrile and the like
  • the fiuorinated 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 the 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 propor-
  • the reaction is carried out in an acetone medium.
  • Acetone is a solvent for the starting materials and the desired product, but does not dissolve the by-product salt.
  • 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 amide 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 by-product amide salt can be reconverted to the fiuorinated polyamide starting material in known manner by treatment with an appropriate ion exchange resin, or by treatment with an aqueous base, such as aqueous sodium hydroxide.
  • 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 Rf group is a perfiuoroalkyl group, it may be straight-chain or branchedchain, preferably containing from 6 to 14 carbon atoms.
  • R radical of the compounds of the present invention include the following:
  • R y and Y have the aforestated meanings and x is an integer from 2 to 4 constitute preferred embodiments of the present invention, those wherein Y is wherein q is an integer from 1 to 6, more preferably from 1 to 3, and wherein hal is a halogen selected from the group consisting of chlorine and bromine being more preferred yet.
  • 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 to 10, with proviso that the sum of m and n is from 1 to 10, and wherein X and p have the aforestated meanlugs.
  • the 1,7-bis(perfiuorooctanoyl) 1,4,7 triazaheptane reactant is prepared as follows:
  • 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 the addition of the n-perfiuorooctanoyl 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.
  • Example 1 is repeated using 9.0 g. (0.01 mol) of 1,7 bis(perfiuorooctanoyl) 1,4,7 triazaheptane, 0.76 ml. (0.01 mol) of chloroacetyl chloride and ml. of acetone. Before charging the chloroacetyl chloride to the reaction mixture there is suspended in the reaction mixture 3.0 g. (0.036 mol) of sodium bicarbonate. The reaction is allowed to proceed under constant agitation for a 3 hour period at l0l5 C. The reaction mixture is then worked up as described in Example 1 to provide 5.0 g. (54% conversion) of the desired product.
  • Example 1 is repeated using 2.12 g. (0.015 mol) of 4-ch1orobutyryl chloride, 27.0 g. (0.03 mol) of 1,7-bis- (perfiuorooctanoyl) 1,4,7 triazaheptane and 375 ml. of acetone to yield 7.0 g. (23% conversion) of 1,7- bis(perfiuorooctanoyl) 4 (4 chlorobutyryl)-1,4,7- triazaheptane product. A portion of that product is recrystallized from acetonitrile to obtain an analytical sample, M.P. 125126 C. Elemental analysis of the analytical sample compares with calculated values for C24H1603N3F30CI as follows:
  • oiland Water-repellent compounds of the invention 0-0 H C lBr by reaction of 1,1 3-bis [perfiuoro (3 -oxa-4-methylpentanoyl) 4- (6-hydr0xyhexyl)-10-methyl)-l,4,7,10,13penta azatridecane with chlorobromoacetyl fluoride.
  • the fluorocarbon derivatives of the invention are especially useful in the treatment of fabrics and fibers comprised of cellulose 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 permanent press, 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 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 oil-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 concentrar'ion of the fluorocarbon derivative on the treated article generally may vary from about 0.5% to 10%, 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 inert to the repellent and capable of dissolution of the requisite amount of oiland waterrepellency 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 a crosslinking catalyst for crosslinking resins with cellulosic materials.
  • the fluorocarbon derivatives of the present invention respond to basic as Well as acidic catalysts, thus have the decided advantage that their use is compatible with perma nent 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, suflicient to retain on the cellulosic material about 1 to 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 100 C. to 165 C. for a time period varying inversely with the temperature ranging from about minutes to 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.
  • the cellulosic material may be first impregnated with an aqueous dispersion 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 dispersion or emulsion of the fluorocarbon derivative together with the catalyst prior to impregnation of the cellulosic material.
  • suitable basic catalyst should have a disassociation constant in Water of at least l.8 l0 at 25 C.
  • Phosphates, carbonates and hydroxides of alkali metals such as sodium phosphate, sodium carbonate, sodium hydroxide and potassium hydroxide; alkaline-earth metal hydroxide including calcium hydroxide and magnesium hydroxide; and quarternary 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.
  • aqueous potassium carbonate solution was sub- (d) Same as (b) above, except that water was substituted for the 5% aqueous sodium hydroxide solution.
  • Papers having a Kit Number of or below will exhibit only fair oil-repellency; those papers having a Kit Number of 8 to 10 will have good oil-repellency; and those having a Kit Number of 10 or above will have excellent oil-repellency.
  • Water-repellency of the treated paper was determined by the so-called Cobb Size mehod, TAPPI Standard T- 441.
  • a weighed specimen of paper is placed under a metal ring of known area. Water is placed in the ring and is allowed to stand on the face of the test paper for 3 minutes. The water is then decanted, the paper specimen is blotted to remove free surface water and is Weighed to determine the amount of Water absorbed. Results are reported in terms of grams of water absorbed per square meter of exposed surface. Papers having a Cobb Size number of 40 to 60 have a fair water-repellency, those having a Cobb Size number of 30 to 40 have good water-repellency, and those having a Cobb Size number of 30 or lower have excellent water-repellency.
  • the resistance of the treated paper to ink penetration is determined by TAPPI Routine Control Method RC-14. In that method a 1.5 in. square piece of the paper, its edges turned up, is floated on standard writing ink (Schaefiers Skrip Permanent Blue-Black Ink #232 was used in these tests), and the time required for the ink to evenly penetrate to the upper surface of the paper is measured in seconds.
  • Specimen A 1,7,-bis(perfluorooctanoyl)-4-chloroacetyl-1,4,7- triazaheptane applied to unsized handsheets.
  • Specimen B 1,7-bis(pertluorooctanoyl)-4-(4-ch1orohutyryl)-1,4,7- triazaheptane applied to unsized handsheets.
  • Specimen C 1,7-bis (perfiuorooctanoyl) 4-(4'chl0robutyry1)-1,4,7- riazaheptane applied to internally rosin sized handsheets.
  • Fluorocarbon compounds having the structural formula R( 5l I(C;H2;-l q) -(3xH2;-I'Z wherein (1) R is a radical selected from the group consisting of (a) perfluoroalkyl having from 5 to 15 carbon carbon atoms, and (b) a radical having the formula wherein (i) m an n are integers of from 0 to 5, with the proviso that the sum of m and n is from 0 to 10, and provided further that when r is 0, m is at least 1,
  • 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,
  • (2) x is an integer from 2 to 4
  • -(3) y is an integer from 1 to 3
  • Z is a member selected from the g1 oup consisting of (a) hydrogen, b) alkyl having 6 carbon atoms, (0) a radical having the formula --ROH where R is a divalent alkylene bridging group containing 6 carbon atoms, (d) a fluorinated acyl radical having the formula wherein R; has the afore-stated meaning, and (e) a haloalkanoyl radical having the formula 0 ll CY wherein Y is a haloalkyl radical having from 1 to 6 car-hon atoms containing from 1 to 2 halogen atoms selected from the group consisting of chlorine and bromine and (5) 2', which may be the same or diiferent in different Z!
  • (C;H2;1 I)- groups is a member selected from the group consisting of (a) alkyl having from 1 to 2 carbon atoms, (b) a radical having the formula ROH wherein R has the afore-stated meaning, (c) a fluorinated acyl radical having the formula 0 (JRi wherein R; has the afore-stated meaning, (d) a haloalkanoyl radical having the formula 0 ll -o-Y wherein Y has the afore-stated meaning and 21 (e) a radical having the formula XH2X N Z 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 H xH2xI I-Z wherein Z is a fiuorinated acyl radical, and at least one of Z or Z is a haloal'kan
  • R is a perfluoroalkyl radical having from 6 to 14 carbon atoms.
  • Y is -C H hal wherein q is an integer from 1 to 6 and hal is a halogen selected from the group consisting of chlorine and bromine.
  • a compound according to claim 14 having the structural formula 0 [(C Fa)2C F O-(C Fz) C ONHC2H4]2N-l%-CH2C1 16.
  • a compound according to claim 14 having the structural formula References Cited UNITED STATES PATENTS 2,528,274 10/1950 Gunderson 260-404.5 2,593,737 4/1952 Diesslin et a1. 260-514 2,950,211 8/1960 Huber et a1 260-404.5 3,038,820 6/ 1962 Albrecht 260-404.5 3,420,697 1/ 1969 Sweeney et a1. 260-404.5 3,446,570 5/1969 Sweeney et a1.
  • 260-404.5 3,453,333 7/1969 Litt et a1.
  • 260-633 3,470,256 9/1969 Evans et a1.
  • haloalkanol should be -haloalkanoyl--.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US749321A 1968-08-01 1968-08-01 Haloalkanoyl derivatives of fluorinated amides Expired - Lifetime US3576017A (en)

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US74930168A 1968-08-01 1968-08-01
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US749310A Expired - Lifetime US3576018A (en) 1968-08-01 1968-08-01 Acrylyl derivatives of fluorinated amides
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5035841A (en) * 1989-05-02 1991-07-30 Air Products And Chemicals, Inc. Triblock amide fluorosurfactants
US20080039605A1 (en) * 2006-08-08 2008-02-14 Weiming Qiu Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1308639B1 (it) * 1999-03-03 2002-01-09 Ausimont Spa Composti triazinici fluorurati.
CN106905197A (zh) * 2017-03-08 2017-06-30 江苏理文化工有限公司 一种含氟丙烯酰胺及其合成方法

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* Cited by examiner, † Cited by third party
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CH473887A (de) * 1966-04-12 1969-06-15 Ciba Geigy Verfahren zum Härten von Gelatine

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5035841A (en) * 1989-05-02 1991-07-30 Air Products And Chemicals, Inc. Triblock amide fluorosurfactants
US20080039605A1 (en) * 2006-08-08 2008-02-14 Weiming Qiu Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
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
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
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

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