US3651069A - Fluorocarbon derivatives - Google Patents

Fluorocarbon derivatives Download PDF

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US3651069A
US3651069A US749350A US3651069DA US3651069A US 3651069 A US3651069 A US 3651069A US 749350 A US749350 A US 749350A US 3651069D A US3651069D A US 3651069DA US 3651069 A US3651069 A US 3651069A
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radical
formula
sulfone
fluorinated
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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

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  • This invention is directed to a new class of fluorocarbon derivatives and to their application to textiles, paper, and like fibrous materials to produce oiland water-repellent products.
  • fluorochemicals have heretofore been employed in the treatment of textiles and paper to impart thereto oiland water-repellency properties.
  • these fluorochemicals are composed of a fluorinated alkyl chain afiixed 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.
  • the 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 also determines the durability of the oleophobic and hydrophobic properties when the treated substrate surface is exposed to repeated laundering and dry cleaning treatments.
  • a high degree of durability of oleophobic and hydrophobic properties is highly desirable for obvious reasons.
  • the portion of the molecule to which the fluorinated alkyl chain is affixed determines, in part, the solubility characteristics of these fluorochemicals.
  • oiland water repellency agents are applied to the substrate in diluted form from a liquid medium which, for reasons of economy, is preferably an aqueous medium.
  • Most known fluorochemical repellency agents are insoluble in water, and for that reason cannot be applied from an aqueous solution, but must be applied from aqueous emulsions. Such emulsions,
  • the portion of the molecule to which the fluorinated alkyl chain is aflixed determines, at least in part the type of catalyst, e.g. acid or base catalyst, if any, that may suitably be employed to effect bonding of the repellent to the substrates, particularly cellnlosic sub strates.
  • catalyst e.g. acid or base catalyst, if any
  • Cellulosic fabrics, in addition to repellency treatment, are often subjected to various other treatments enhancing their properties, such as permanent press treatments and wrinkle-resistance treatments. These other treatments commonly involve use of acidic or basic catalysts and/or reagents.
  • Fluorochemical repellents which are responsive to both acidic ac well as basic catalysts provide for flexibiilty in application in that they are compatible with other treatments involving both acidic or basic conditions. For these and other reasons favorable response to both acidic as well as basic catalysts is a highly desirable property in repellency agents.
  • one object of the present invention is the provision of novel fluorocarbon derivatives.
  • a further object is the provision of water soluble or water dispersible repellency agents suitable for bonding to cellulosic materials, using both acidic and basic catalysts to impart thereto hydrophobic and/or oleophobic properties.
  • a still further object is the provision of textile and paper materials treated with the fluorocarbon derivatives of the present invention.
  • An additional object is the provision of cellulosic materials chemically modified with the novel fluorocarbon derivatives of the present invention.
  • novel fluorinated quaternary ammonium salts of the present invention have the formula wherein (1) R is a radical selected from the group consisting of (a) perfluoroalkyl having from 3 to 17 carbon atoms, and
  • R and R are fluorine or are fiuoroalkyl 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 are each integers of from to 20, with the proviso that the sum of m and n is from 0 to 20, and provided further that when v is 0, m is at least 1,
  • n 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,
  • (v) v is 0 or 1, with the proviso that when the sum of m, n and u is greater than 0, then 1 is always 0,
  • R is hydrogen, an alkyl, an aryl or a substituted aryl radical, and (d) a sulfone-tertiary amine adduct radical having the formula wherein p, R and R have the afore-stated meanings and wherein X, X and X collectively represent the residue of the pyridine, methyl-substituted pyridine or quinoline ring systems,
  • Z which may be the same or different in different groups, is a member selected from the group consisting of (a) hydrogen,
  • X is a negatively charged ion selected from the group consisting of a halide ion, a sulfate anion, an acid sulfate anion, a phosphate anion and an acid phosphate anion,
  • q is a whole number from 1 to 4 corresponding to the number of sulfone-tertiary amine adduct radicals present in the molecule
  • r is a whole number from 1 to 3 corresponding to the valency of the negatively charged ion
  • At least one of Z and Z' is an acyl radical or Z is a radical having the formula H -C;Hg;l I-Z wherein Z is an acyl radical and at least one of Z and Z is a sulfone-tertiary amine adduct radical or Z is a radical having the formula H C;HQX1 ⁇ ITZ wherein Z is a sulfone-tertiary amine adduct radical, said acyl and sulfone-tertiary amine adduct radicals having the afore-stated formulas.
  • the alkylene C,,'H linkage may be a straight-chain or branched-chain group, preferably containing from 2 to 4 carbon atoms.
  • R may be a straight-chain or branched-chain alkylene radical containing from 1 to 4 carbon atoms; an aryl radical such as phenyl or naphthyl; or an aralkyl radical such as benzyl, phenethyl or xylyl.
  • R moy be an alkyl radical containing from 1 to 6 carbon atoms including methyl, ethyl, propyl, hexyl as well as various isomeric forms thereof; or an aryl radical such as phenyl, naphthyl and substituted derivatives thereof, including ortho-, metaor para-tolyl; ortho-, metaor para-chlorophenyl and paranitrophenyl.
  • the fluorinated quaternary ammonium salts of the present invention may be prepared by reacting a corresponding divinyl sulfone adduct reactant with a heterocyclic tertiary amine salt of a salt-forming acid.
  • the divinyl sulfone adduct reactant has the formula 1 'i') H R;( N- exnhn Fermio (11) wherein R,, x and y have the afore-stated meanings,
  • Q is a member selected from the group consisting of hydrogen, an acyl radical having the formula [REEL 5 ll wherein R, R and p have the afore-stated meanings
  • heterocyclic amine salts of salt-forming acids suitable for reaction with the above-described divinyl sulfone adduct reactants to yield the novel fiuorinated quaternary ammonium salts of the present invention are the halides, i.e. fluorides, chlorides, bromides, iodides, the sulfates or the phosphates of pyridine, the methyl-substituted pyridines, i.e. the picolines, lutidines and the collidines, and quinoline.
  • the divinyl sulfone adduct reactants of Formula II, above, may be prepared by reacting a corresponding fluorinated polyamide reactant with a vinyl sulfone reactant.
  • the vinyl sulfone reactant employed in the preparation of the divinyl sulfone adduct reactant of Formula H, above, may be substituted or unsubstituted and, when substituted, has only one substituent on each vinyl group.
  • the vinyl sulfone reactant is represented by the formula v R R o o R R u I: lg] H CS R -C CH t) l) (111) wherein R, R and p are as previously defined.
  • vinyl sulfone reactants include divinyl sulfone; dipropenyl sulfone; diisopropenyl sulfone; distyryl sulfone; bis(1-hexeny1) sulfone; bis(alpha-ethylvinyl) sulfone; bis(alpha-nbutylvinyl) sulfone; bis(alpha-phenylvinyl) sulfone; 1,2-bis (vinylsulfonyl) ethane; 1,2-bis (styryl sulfonyl) ethane; l,4-bis(alpha-ethylvinyl sulfonyl) butane; and 1,4-bis(vinyl sulfonyl) benzene and the like.
  • the fluorinated polyamide reactant suitable for reaction with the vinyl sulfone reactant of Formula 111, above, to prepare the divinyl sulfone adduct reactants of Formula II, above, is characterized by the structural formula wherein R x and y have the above-stated meanings, Y is a member selected from the group consisting of hydrogen and an acyl radical having the formula ll --CRt in which R; has the afore-stated meaning and Y 'is a member selected from the group consisting of hydrogen, an acyl radical having the formula in which R has the afore-stated meaning and a radical having the formula in which x and Y have the afore-stated meanings, provided that at least one of Y and Y is an acyl radical or Y is a radical having the formula in which Y is an acyl radical, said acyl radical having the afore-stated formula, and at least one of Y and Y is hydrogen.
  • the fluorinated polyamide reactant of Formula IV is prepared by reaction of a fluorine-containing carboxylic acid having the formula R COO'H, wherein R: has the afore-stated meaning, or a derivate thereof such as an ester, anhydride or acid halide thereof with a polyalkylene polyamine corresponding to the formula NH (C H ,l I) CxH2xN 2 wherein x and y have the afore-stated meanings and E is hydrogen or an aminoalkyl radical having the formula -C H NH wherein x has the afore-stated meaning.
  • the polyalklylene polyamine reactants employed in the preparation of the fiuorinated polyamide reactants of Formula IV, above, are known compounds. These reactants may be straight-chain 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 poly-amines containing from 3 to 6 nitrogen atoms in the molecule.
  • polyaklene polyamines 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, tetraethylene pentamine, tetra-npropylene pentamine, tetra-n-butylene pentamine, 4 (2- aminoethyl)-l,4,7 tetraazadecane, tetra-n-hexylene pentamine and pentaethylene hexamine.
  • Fluorine-containing carboxylic acid reactants, above described, wherein R is perfluoroalkyl, suitable for the preparation of fluorinated polyamide reactants of Formula IV, above, comprise perfluorocarboxylic acids, esters, anhydrides or acid halides thereof.
  • Perfiuorocarboxylic acid reactants suitable for reaction with the above poly-alkylene polyamine reactants are saturated straight-chain or branched-chain monocarboxylic acids or stated derivatives thereof containing from 4 to 18, preferably from 6 to 14, 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, perfluorocaproic, 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 fiuorination 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.
  • Fluorine-containing carboxylic acid reactants above described, wherein R is a radical having the formula w re wherein R1, R M, v, n, m and u have the afore-stated meanings may be prepared by various hereinafter de scribed methods.
  • telomers having the general formula wherein R and R have the afore-stated meanings, wherein s and t are each integers from to 20, the sum of s and t 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.
  • these telomers are prepared by radical addition reactions of polyfiuoroisoalkoxyalkyl halide telogens of the formula wherein R and 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, eg CsF, to form a fluorinated organic salt and then reacting the organic salt with a halogen other than fluorine or chlorine and tetrafluoroethylene.
  • a halogen other than fluorine or chlorine and tetrafluoroethylene 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, the pertinent subject matter of which applications is hereby incorporated by reference.
  • Fluorine-containing carboxylic acids of the formula RgCOOH wherein R; has the formula VI, above, wherein v, n and u are all 0 and wherein m is at least 2 may be prepared by reacting the corresponding telomer represented by general Formula VII, 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 superatrnospheric pressure 'above about 20 to 200 atmospheres or more at temperatures in excess of about 300 0., 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.
  • Fluorine-containing carboxylic acids of the formula R COOH wherein R: has the Formula VI, above, wherein m is at least 1, v and u are both 0 and n is greater than 0 may be prepared by reacting the corresponding telomer represented by Formula VII, 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 temperature between about 60 and about C.
  • Fluorine-containing carboxylic acids of the formula R COOH wherein R has the Formula VI, above, wherein m is at least 1, v is 0, u is 1 and M is hydrogen can be prepared by reacting the corresponding telomer represented by general Formula VII, 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.
  • Fluorine-containing carboxylic acids of the formula R COOH wherein R: has the Formula VI, above, wherein m is at least 1, v and n are both 0, u is 1 and M is fluorine can be prepared by reacting a corresponding telomer represented by Formula VII, above, wherein t is O with S0 to form corresponding acid halides and fluoropyrosulfates, and hydrolyzing the acid halides and fiuoropyrosulfates by refluxing with water to obtain the corresponding free acids.
  • Fluorine-containing carboxylic acids of the formula R COOH wherein Rf has the Formula VI, above, wherein v is 1 and m, n and u are all 0 can be prepared by the same method from polyfluoroisoalkoxyalkyl halide compounds of Formula VIII above.
  • Fluorine-containing carboxylic acids of the Formula R COOH wherein R; has the Formula VI, above, wherein m is 1 and v, n and u are all 0 can be prepared from polyfluoroisoalkoxyalkyl halide compounds of Formula VIII, 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. 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, referred to above.
  • esters and acid halides of the above-described acids may be prepared from the acids by conventional procedures.
  • telomers of Formula VII, above, and the fluorine-containing 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 fluorine-containing 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.
  • R group is a fluorinated isoalkoxyalkl group represented by Formula VI, above then, in the moiety of the R radical of Formula VI, above, include the following:
  • the fluorinated polyamide reactant of Formula IV may be prepared by simply mixing the fluorinecontaining carboxylic acid reactant with the polyalkyl ene polyamine reactant. These reactants may be charged in a molar proportion of 1 mol of polyalkylene polyamine reactant to about 0.5 to 7 mols of fluorine-containing 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 may be recovered from the reaction mixture by methods known to those skilled in the art.
  • the fluorinated polyamide obtained as a result of the reaction of the fluorine-containing carboxylic acid reactant with the polyalkylene polyamine reactant above described may comprise a single compound conforming to 7 Formula IV, above, a mixture of isomers thereof or a reaction mass composed of amide products containing two or more amide functions.
  • the resulting fluorinated polyamide is suitable without further purification for reaction with the vinyl sulfone reactant of Formula HI, above, to
  • the fluorinated polyamide may be further purified prior to reaction with the vinyl sulfone reactant as by distillation or recrystallization.
  • the divinyl sulfone adduct reactant of Formula II above may be prepared by heating a mixture of the sulfone reactant of Formula III above, with the fluorinated polyamide above-described. These reactants may be charged in a mol proportion of 1 mol of fluorinated polyamide to about 1 to 10 mols of sulfone reactant.
  • the reaction temperature and time are dependent upon the particular fluorinated polyamide and sulfone reactants involved. The temperature ranges from about 25 C. to 160 C., and the time ranges from about /2 to 4 hours. If desired, the reaction may be conducted in the presence of an inert organic solvent.
  • the resulting divinyl sulfone adduct may be recovered from the reaction mixture by conventional methods.
  • novel fluorinated quaternary ammonium salts of the present invention may be prepared by simply mixing the divinyl sulfone adduct reactant with the heterocyclic tertiary amine salt of a salt-forming acid, or alternatively, by mixing the divinyl sulfone adduct reactant with the heterocyclic tertiary amine and the salt-forming acid. These reactions are preferably carried out in the presence of a suitable inert organic solvent. These reactants may be charged in a molar proportion of 1 mol of divinyl sulfone adduct reactant to about 1 to 15, preferably about 5 to 10 mols of heterocyclic tertiary amine salt reactant.
  • the heterocyclic tertiary amine and the salt-forming acid are charged separately, then it is preferred to employ a slight excess of the heterocyclic tertiary amine, say between about 1.1 to 1.8 mols of heterocyclic tertiary amine per mol of salt-forming acid.
  • the reaction temperature and time are dependent upon the particular divinyl sulfone and heterocyclic tertiary amine salt reactants involved. The temperature varies from about 25 C. to C., preferably about 50 C. to 75 C., and the time ranges from about 5 minutes to about 24 hours.
  • the reaction is preferably conducted in the presence of an inert organic solvent or solvent mixture.
  • the lower aliphatic ketones and alcohols are exemplary of suitable inert organic solvents.
  • the maximum temperature is limited only by the reflux temperature of the reaction mixture.
  • the reaction may be conducted at superatmospheric pressure, it is preferred to conduct the reaction at atmospheric pressure.
  • the reaction may be carried out in the presence of a tertiary aliphatic amine catalyst.
  • exemplary suitable tertiary aliphatic amine catalysts are triethylamine, tripropylamine, tributylamine, and the like. Triethylamine is a preferred catalyst.
  • the tertiary aliphatic amine catalyst, if one is employed, is used in amount of between about 0.1% and about 1.0% of the combined weight of the reaction mixture.
  • the sought-for fluorinated quaternary ammonium salt product may be recovered from the reaction mixture by evaporation of solvent therefrom to obtain the crude product as the residue, or by cooling the mixture to precipitate the product which may then be recovered by filtration.
  • the product thus obtained is suitable for use as oiland Water-repellency agent without further purification.
  • the fluorinated quaternary ammonium salt so produced may be further purified prior to use, as by recrystallization using any commonly employed inert organic solvent, such as acetonitrile, ethanol or isopropanol.
  • Preferred fluorinated quaternary ammonium salts of the present invention correspond to the general formula OH H 11 wherein R;, x and y have the aforestated meanings and wherein X represents a halide ion, most preferable a chloride ion.
  • a specific class of preferred embodiments of the present invention are fluorinated quaternary ammonium salts according to Formula IX, above, wherein the R; radica has the formula
  • To a solution of 15.18 g. (0.015 mol) of 1,7-bis(perfluorooctanoyl) 4 (2 vinylsulfonylethyl) 1,4,7 triazaheptane in 50 ml. of acetone are added drops of triethylamine (as catalyst).
  • Into this solution is dropped a mixture of 8.28 g. (0.1 mol) of pyridine, 5.04 ml. of 12 N hydrochloric acid and ml. of ethanol. The mixture thus obtained is stirred and refluxed for a period of 3 hours.
  • the 1,7 bis(perfluorooctanoyl) 4 (2-vinylsulfonylethyl)-1,4,7-triazaheptane reactant is prepared as follows:
  • Solid 1,7 bis(perfluorooctanoyl) 1,4,7-triazaheptane (2.4 g.) is heated at 130 C. to 140 C. in ml. of dimethylformamide until all of the solid dissolves.
  • To this solution is added 2 ml. of divinyl sulfone, and the resulting reaction mixture is heated to 140 C. for 3 hours.
  • the reaction product is cooled to room temperature and is transferred to a separatory funnel. Thereafter, 25 ml. of water is added and a yellow water-insoluble oil layer is formed.
  • the oily product is extracted with two 25 ml. portions of diethyl ether, the ether extracts are combined, washed with two 25 ml.
  • a solution of 49 g. (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 g. (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 nperfluorooctanoyl 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 mixture is then cooled for 1 hour in an ice-bath to precipitate the crude 1,10-bis(perfluorooctanoyl) 4,7 bis[2 (2 pyridiniumethylsulfonyl) ethyl] 1,4,7,10 tetraazadecane dichloride product.
  • the crude product is recovered by filtration and is recrystallized from acetonitrile to yield 15 g. of product, M.P. -165 C. Upon further recrystallization (twice) from acetonitrile, the product has a melting point of 175 C. The product is soluble in water.
  • the 1,10 bis(perfluorooctanoyl) 4,7 bis(2 vinylsulfonylethyl) 1,4,7,10 tetraazadecane reactant is prepared as follows:
  • the perfluoroalkyl diamide reactant is prepared in the by reaction of following manner: 0
  • the invention is also appliwith quinoline hydrochloride.
  • cable to the treatment of blends of natural and/ or syn- (cFmOFo-(oFz)100NH(G2HrN)2C2H4NHo0-(0F2)1--ooF(oF HgCHzSOgCHzCHz-N O CH; by reaction of (CF9 0FO-(CF --CONH(C2H4N)QCQH4NHC0-(CFz)1OCF(CF H2GHzSOzCH CHz with Y PY idine dihydl'ogen P P thetic fibers in cloth, for example, blends containing poly- 0 f ethylene terephthalate, polyacrylonitrile, nylon, cotton J N 0H,C C,F,, e and wool.
  • auxiliary agents such as those im- 3C1 parting crease resistance, permanent press properties and HZCHZSO2CH2CHPN O softening properties may be applied in conjunction with 40 the fluorinated quaternary ammonium salts of the invenby reactlon of I tion.
  • the fluorinated quaternary ammonium salts of the 0 I present invention may be applied to the article to be C F N-CH CH OH -NCH CH;CH c rendered roll-repellent by treating the same with a solu- CHZCHZSOZCHZCHZ tron or d1spers1on of the repellent and evaporating the with pyridine hydrochloride I solvent or dispersant.
  • the concentration of the oiland water-repellent compound on the treated article generally may vary from about 0.5% to 20%, preferably 1.0% to 10.0%, based on the weight of the article. Since the fluorinated quaternary ammonium salts of the present invention are soluble or dispersible in water, they are preferably applied from an aqueous solution or an aqueous dispersion, although, if desired, any organic liquid inert to the article to be treated and capable of dissolving or dispersing the requisite amount of oiland water-repellency agent may be employed.
  • Acetone, methyl ethyl ketone, acetonitrile and dimethylformamide are illustrative organic liquids which may be used in preparing oiland Water-repellent compositions comprising fiuorinated quaternary ammonium salts of the present invention.
  • the solvent or dispersant may be evaporated by air drying at room temperature. If it is desired to cure the treated articles the solvent or dispersant may be evaporated prior to curing or during curing of the oiland water-repellent chemical onto the articles.
  • the article treated with a solution or dispersion of the fluorinated quaternary ammonium salt is air dried prior to curing for a time sufficient to evaporate essentially all of the solvent or dispersant. 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 fluorinated quaternary ammonium salts of the present invention are preferably applied thereto from an aqueous solution or an aqueous dispersion and in the presence of a catalyst of the type commonly used as crosslinking catalyst for crosslinking resins with cellulose materials.
  • the fluorinated quaternary ammonium salts of the present invention respond well to both basic and acidic catalysts, thus offer the decided advantage that their application is compatible with permanent press treatment of textiles, which treatment commonly employs acidic reactants and/or catalysts.
  • the cellulosic textile material is moistened with an aqueous solution of the catalyst, air dried to remove residual water and then impregnated with an aqueous solution or dispersion of the fluorinated quaternary ammonium salt of the invention for a time, normally 30 seconds to about 30 minutes, sufficient to retain on the cellulosic textile material about 1 to 20%, preferably 2 to 8% of the oiland water-repellency agent, based on the weight of the cellulosic textile material.
  • the thusly impregnated cellulosic textile 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 30 seconds.
  • the chemically modified cellulosic textile material is washed free of excess catalyst with water and dried.
  • the cellulosic textile material may be first impregnated with an aqueous solution or dispersion of the fluorinated quaternary ammonium salt, then treated with an aqueous solution of the catalyst, air dried and finally heated to effect reaction of the fluorinated quaternary ammonium salt with the cellulosic material.
  • Another modification of the above-described procedure involves premixing the aqueous solution or dispersion of the fluorinated quaternary ammonium salt together with the catalyst prior to impregna tion of the cellulosic textile material.
  • suitable basic catalyst should have a dissociation 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 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 catalyst, ammonium chloride, magnesium chloride, zinc nitrate and zinc chloride being specific examples of preferred acid catalysts.
  • the catalyst concentration is normally depend- I ent upon the strength of the acid or base 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.
  • Hydrophobic properties of the treated cloth were determined by Method 22-1961 of the American Association of Textile Chemists and Colorists which is described, for example, on pages 152-153 of the Technical Manual and Yearbook of that association for the year 1961. It is to be noted that this method provides for no interpolation of results which are reported as one of the Standard Spray Test ratings which are the six ratings 0, 50, 70, 80, and 100.
  • Wash fastness of the treated cloth was determined by subjecting the cloth to repeated launderings in hot water in a household automatic washing machine using a heavy duty detergent, followed by drying in an automatic household drier. The material was ironed prior to testing.
  • Table III shows the compositions of the oil mixtures and corresponding Kit Numbers.
  • the fluorinated quaternary ammonium salts of the present invention may be applied thereto either externally, as by treating the paper with a solution or Castor oil Toluene Heptane dispersion of the repellent and evaporating the solvent or dispersant in the manner described above, or the repellent 08 0 0 may be applied thereto internally, as by adding the re- 3 pellent to the furnish from which the paper is to be 38 30 so formed, and then forming the paper in the usual manner.
  • the fluorinated quaternary ammo- 2 g8 g8 nium salts of the present invention are suitably added to g 93 the furnish in amount of between about 2% and about 40 0 90 110 4%, dry weight basis, preferably between about .5 and about 2%, dry weight basis.
  • the repellent may be added to the furnish neat or in form of its solution or suspension in water or one of the above-described solvents or dispersants.
  • the repellent may be added to the furnish together with any of the usual additives, such as fillers, e.g. kaolin, China clay, calcium carbonate, titanium dioxide; sizes, e.g. rosin, hydrocarbon and natural waxes, natural gums, starches, casein, asphalt emulsions, synthetic resins, cellulose derivatives; coloring matter, e.g. dyes and pigments; and alum.
  • fillers e.g. kaolin, China clay, calcium carbonate, titanium dioxide
  • sizes e.g. rosin, hydrocarbon and natural waxes, natural gums, starches, casein, asphalt emulsions, synthetic resins, cellulose derivatives
  • coloring matter e.g. dyes and pigments
  • alum e.g. dyes and pigments
  • Oil-repellency tests on paper specimens rendered oilrepellent by both external and internal treatment with an illustrative fluorinated quaternary ammonium salt of the present invention are described below.
  • 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 Papers having a Kit Number of about 5-6 or below will exhibit only fair oil-repellency; those papers having a Kit Number of 8-10 will have good oil-repellency; and those having a Kit Number of 10 or above will have excellent oil-repellency.
  • This slurry was diluted to 0.40% consistency, the 1,7-bis (perfluorooctanoyl) 4 [2-(2-pyridiniumethylsnlfonyl) ethyl]-l,4,7-triazaheptane repellent was added in form of its aqueous solution in predetermined amounts, the slurry was agitated by slow stirring to evenly distribute the repellent solution in the slurry, and the slurry was divided into three equal portions. Each of these portions was then diluted to 0.05% consistency, and each portion s0 diluted was fed to a Williams handsheet mold to form 7% x 7 /2 in. handsheets.
  • 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 v is 0, m is at least 1,
  • M is selected from the group consisting of hydrogen and fluorine, with the proviso that when n is greater than 0, then M is always hydrogen,
  • (v) v is 0 or 1, with the proviso that when the sum of m, n and u is greater than 0, then v is always 0,
  • q is a whole number from 1 to 4 corresponding to the number of sulfone-tertiary amine adduct radicals present in the molecule
  • r is a whole number from 1 to 3 corresponding to the valency of the negatively charged ion, with the proviso that Z is an acyl radical or Z is a radical having the formula wherein Z is an acyl radical and in at least one occurrence Z is a sulfone-tertiary amine adduct radical,
  • R is a perfluoroalkyl radical containing from 6 to 14 carbon atoms, x is an integer from 2 to 4 and y is an integer from 1 to 4.
  • X represents a halide ion
  • R is a radical having 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 M and u have the meanings stated in claim 9.

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3896035A (en) * 1973-04-02 1975-07-22 Minnesota Mining & Mfg Pile fabric treating composition providing soil resistance
US20080039605A1 (en) * 2006-08-08 2008-02-14 Weiming Qiu Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
US8771470B2 (en) * 2012-01-17 2014-07-08 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
CN109235030A (zh) * 2018-08-21 2019-01-18 湖南工程学院 一种含有活性基团的含氟涂层整理剂及其合成方法和应用

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3896035A (en) * 1973-04-02 1975-07-22 Minnesota Mining & Mfg Pile fabric treating composition providing soil resistance
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
US8771470B2 (en) * 2012-01-17 2014-07-08 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
US9133584B2 (en) 2012-01-17 2015-09-15 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
US9499943B2 (en) 2012-01-17 2016-11-22 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
CN109235030A (zh) * 2018-08-21 2019-01-18 湖南工程学院 一种含有活性基团的含氟涂层整理剂及其合成方法和应用

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