US3147066A

US3147066A - Quaternized perfluoroalkane sulfonamido nu-halomethyl carboxylic amides and a process for treating textiles therewith

Info

Publication number: US3147066A
Application number: US25901A
Authority: US
Inventors: Harvey A Brown; Robert J Koshar
Original assignee: Minnesota Mining and Manufacturing Co
Current assignee: 3M Co
Priority date: 1960-05-02
Filing date: 1960-05-02
Publication date: 1964-09-01
Anticipated expiration: 1981-09-01

Description

United States Patent .0,

QUATERNIZED PERFLUQROALKANE SULFONA- MIDO N-HALQMETHYL CARBOXYLIC AMIDES AND A PROCESS FOR TREATWG TEXTILES THEREWITH Harvey A. Brown, East Oakdale Township, Washington County, and Robert J. Koshar, Lincoln Township, Washington County, Minn., assignors to Minnesota Mining and Manufacturing Company, St. Paul, Minn, a corporation of Delaware No Drawing. Filed May 2, 1960, Ser. No. 25,901 5 Claims. (Cl. 8116.2)

This invention relates to quaternized halomethylamides and more particularly to certain new quaternized perfluoroalkanesulfonamido N-halomethyl carboxylic amides, and to a process for rendering textiles soil-resistant as well as oil and water repellent.

The novel quaternized halomethyl amides of the invention contain a quaternary ammonium group attached to a perfiuoroalkyl group through a sulfonamido-alkylene carboxyarnide radical. The quaternary ammonium group forms the cation of a salt of which the anion is a halide ion. It will be evident that the terms quaternary ammonium group and quaternized N-halomethyl group have reference as to the hydrophilic portion of the molecule and are substantially synonymous. When the perfluoroalkyl group contains from about 4 to about 12 fully fiuorinated carbon atoms, it has been found that the novel compounds of the invention can be employed as textile finishes, and particularly to treat fibrous materials such as cotton, Wool, nylon, silk, rayon, polyacrylate and polyacrylouitrile fibers and the like to produce a soil-resistant, waterand oil-repellent finish for such materials without thereby altering either the color or tensile strength.

While it has heretofore been found possible to produce valuable and useful soil-resistance, and oiland waterrepellency, in wool and certain synthetic fibers, it has been diflicult to produce lasting effects on the cellulosic fibers. The finishes heretofore developed for this purpose, such as those which employ amide-quaternary amines as described in United States Patent No. 2,303,191, have been relatively easily removed, often by a single laundering operation. They have also required the deposit of relatively large amounts of the treating agent on the fibers, as compared with the compositions of the present invention.

It is an object of this invention to provide quaternary ammonium compounds possessing fluorocarbon tails.

Another object of this invention is to provide agents by means of which fibrous materials can be rendered oiland water-repellent.

Another object of this invention is to provide agents by means of which cellulosic materials and particularly cotton fibers can be rendered lastingly oiland waterrepellent.

A further object of this invention is to provide oiland water-repellent cellulosic materials such as cotton cloth.

Still another object of the invention is to provide a process for rendering cellulosic materials soil-resistant.

Other objects will become apparent hereinafter.

In accordance with the above and other objects of this invention certain novel halomethylarnides have been discovered to be useful for the production of quaternary ammonium salts containing a perfluorocarbon tail, and that the resulting quaternized compounds produce lasting 3,147,066 Patented Sept. 1, 1964 ICC oiland water-repellency when applied to cellulosic fabrics and fibers and the like as well as noncellulosic fibers and materials. These quarternary ammonium salts can be represented by the formula:

wherein R, is a pertluoroalkyl group containing 4 to 12 carbon atoms, m is an integer from 2 to 12, R is an alkyl group containing 1 to 6 carbon atoms, Q is a radical of a tertiary nitrogenous base and X is chlorine or bromine.

It is important that the perfluorocarbon tail contain at least four carbon atoms, and the preferred number is six to ten. A terminal fluorocarbon chain of this minimum length is required in order to insolubilize and render the end of the molecule both hydrophobic andoleophobic.

The perfiuorocarbon tail structure may include an oxygen atom linking together two perfluorinated carbon atoms, or a nitrogen atom linking together three perfiuorinated carbon atoms, since these linkages are very stable and do not impair the inert and stable fluorocarbon characteristic of the structure. The R, groups can accordingly be a perfluoroalkyl group (C F a perfluorocycloalkyl group (C F or a substituted perfiuoroalkyl group (C F O or (C F N.

The perfluorocarbon tail of the molecule is inert, non-polar, and is both hydrophobic and oleophobic. It is repellent not only to water but to oils and hydrocarbons, It imparts unique surface active and surface treating properties not possessed by corresponding compounds having a hydrocarbon tail, the latter being oleophilic and highly soluble in oils and hydrocarbons.

It has been found that the quaternized N-(halomethyl) amides of the invention can be applied to woven and nonwoven fabrics as more fully described hereinafter to provide oiland Water-repellency with improved resistance to laundering and dry cleaning.

The quaternized N-(halomethyl)amides of the invention may be used as the sole component in the treating vehicle or as a component in a complex multi-ingredient formulation. For instance, excellent water and oil repellency and soil resistance is obtained on textile fabrics which are treated simultaneously with the quaternized N-(halomethyDamides and conventional finishes, such as mildew preventatives, moth resisting agents, crease resistant resins, lubricants, softeners, sizes, flame retardants, anti-static agents, dye fixatives, and water repellents. In the treatment of paper the quaternized N-(halomethyl) amide may be present as an ingredient in a wax, starch, casein, elastomer or wet strength resin formulation.

In addition to oil and water repellency and soil resist? ance properties, the quaternized N-(halomethyl)amides may be used to impart lower surface adhesion values and lower coefiicients of friction to substrates. Accordingly, they may also be used as mold release agents, for example, on wooden concrete-forms, and related applications.

In the treatment of fabrics and fibrous materials, the quaternized N-(halomethyl)amides of the invention may be employed in conjunction with other treating agents, such as crease resisting resins, sizes, softeners, and water repellents, by concurrent or sequential treatments. Known treating agents of these classes are as follows. Crease resisting resins: Urea-formaldehyde resins, ethylene urea-formaldehyde resins, melamine-formaldehyde resins, triazine-formaldehyde resins, epoxy resins, and polyglycol acetals.

Sizes: Starch, casein, glue, polyvinyl alcohol, polyvinyl acetate, methyl cellulose, carboxymethyl cellulose. Softeners: Polyethylene glycols, polyethylene, dimethyl polysiloxanes, amines and amides derived from fatty acids and ethylene oxide condensation products of such amines and amides.

Water repellents: Waxes, aluminum salts of fatty acids, silicone resins, chromium complexes of fatty acids, Nalkyl amidomethyl pyridinium salts, and melamineformaldehyde resin condensates with amides from fatty acids.

The compounds of the invention are prepared by the action of formaldehyde and hydrogen halide, e.g. hydrogen bromide or hydrogen chloride, on the amide to produce an N-(halomethyl)amide which is not usually isolated but is readily converted to a quaternary ammonium salt directly by addition of a tertiary nitrogenous base such as pyridine. The process is conveniently carried out out by passing the selected anhydrous hydrogen halide in gaseous form into a solution of the amide and paraformaldehyde in an inert solvent, such as toluene, benzene and the like, until there is substantially no further absorption of the hydrogen halide. As the reaction is not strongly exothermic, no temperature control is required, although heating from about 25 C. to 100 C. (depending to an extent on the boiling point of the solvent used) may help to insure completion of the reaction. Although acids are sometimes employed for the cleavage of amides, this does not appear to occur during the reaction even though the strongly acidic hydrogen halides are employed.

The omega-perfluoroalkanesulfonamido-alkanoic acids from which the amides employed as starting materials in the process of the invention are readily available by the procedure described in US. Patent No. 2,809,990 and particularly described in Examples 4 and thereof. The sodium derivative of an N-alkyl-perfluoro-alkanesulfonamide is reacted with an alkyl omega-haloalkanoate to produce the corresponding alkyl omega-perfluoroalkanesulfonamido alkanoate which is found can be ammonolyzed directly to the amide with some difficulty or can be successively saponified, converted to the acid chloride and then to the amide. The omega-bromoalkanoic acids are converted to methyl or other alkyl esters suitable for the above described reaction by conventional methods, such as heating a mixture of the acid and the selected alcohol in the presence of a catalytic amount of sulfuric acid. Illustrative of suitable omega-perfluoroalkanesulfonamidoalkanoic amides which can be produced as described above from the known perfluoroalkanesulfonamidcs and omega-bromoalkanoic acids are:

3 (N-propyl-perfiuorobutanesulfonamido -propanoic amide 3 (N-methyl-perfluorobutanesulfonamido) -propanoic amide 3 (N-butyl-perfiuorooctanesulfonamido -propanoic amide 4- (N-butyl-perfluoro octanesulfonamido -butanoic amide 4- (N-hexyl-perfiuorododecanesulfonamido -butanoic amide 5- (N-methyl-perfiuorooctanesulfonamido) -pentanoic amide 5- (N-amyl-perfluorooctanesulfonamido) -pentanoic amide 6- (N-ethyl-perfiuorobutanesulfonamido -hexanoic amide 6- (N-butyl-p erfluorododecanesulfonamido -l1exanoic amide 7- (N-methyl-perfiuorooctanesulfonamido) -heptanoic amide 9- (N-ethyl-perfiuorobutanesulfonamido -nonanoic amide 11- (N-methyl-perfiuorooctanesulfonamido) -hendecanoic amide I 13- (N-ethyl-perfluorobutanesulfonamido -tridecanoic amide Quaternization is effected without isolation of the intermediate N-(halomethyl)-amide in the inert solvent employed for the reaction after brief evaporation to remove excess hydrogen halide, or the reaction mixture may be further evaporated and some other solvent, such as anhydrous ether or dioxane, in which the quaternary salt is insoluble, may be added. The desired tertiary organic base or amine is then added in the stoichiometric amount while maintaining the reaction in the range of about 25 C. to about C. For this purpose any tertiary nitrogenous organic base which is capable of forming a salt or a quaternary compound is suitable, including, for example, trialkyl amines such as trimethyl-amine, tributylamine and triododecylamine; cycloalkyl amines such as tricyclohexylamine; aralkyl amines such as benzyl dimethylamine; arylamines such as dimethylaniline; and heterocyclic amines such as pyridine, picoline, lutidine, quinoline and the like can be used. Pyridine is particularly preferred for convenience and economy in the formation of cloth-treating agents as shown above.

Another procedure which is very convenient since it avoids the use of hydrogen halide is to react the amide and paraformaldehyde directly with the hydrohalide of the tertiary nitrogenous base, such as pyridine hydrochloride, in a suitable solvent such as the base, e.g., pyridine. Isolation is then carried out as described above adding, if desired, a further amount of an organic solvent, such as an ether, for example, diethylether.

Examples of the quaternary ammonium salts of the perfluoro-alkyl substituted amide compounds of the invention are:

3 (N-propyl) perfluorobutanesulfonamidopropionamidomethyl tributyl ammonium bromide 3 (N-methyl) perfluorobutanesulfonamidopropionamidomethyl pyridinium chloride 4 (N-butyl-pertluorooctanesulfonamido) butanoamidomethyl picolinium bromide 4 (N-hexyl-perfluorododecanesulfonamido) butanoamidomethyl phenyl dimethyl ammonium chloride.

5 (N-methyl) pertluorooctanesulfonamidopentanoamidomethyl quinoliuiurn bromide 5 (N-amyl perfluorooctanesulfonamido) pentanoamidomethyl triethyl ammonium bromide 6 (N-ethyl) perfluorobutanesulfonamidohexanoamidomethyl trimethylammonium chloride 6 (N-butyl) perfiuorododecanesulfonamidohexanoamidomethyl tricyclohexylammonium chloride 7 (N-methyl) perfluorooctanesulfonamidoheptanoamidomethyl pyridinium chloride 9 (N-ethyl-perfiuorobutanesulfonamido) nonanoamidomethyl pyridinium bromide 11 (N-methy1-perfiuorooctanesulfonamido) hendecanamidomethyl pyridinium chloride 13 (N-ethyl perfiuorobutanesulfonamido) tridecanamidomethyl trimethyl ammonium chloride.

The quaternized N-halomethylamides of the invention are employed for treating woven or non-woven fibrous materials including wool, cotton, rayon, acetate, nylon and the like textiles, or paper, leather, wood, felt and similar organic fibrous constructions, and particularly cellulosic materials, by applying the selected quaternary ammonium derivative, in aqueous medium buffered to about a pH in the range of about pH 5.5-6.5 and preferably about pH 6, to the cloth, removing any excess, drying at a temperature in the range of about 40 to 100 C. and heating the dried material to a temperature in the range of about 100 to C. for a period of the order of about 5 to 30 minutes to fix the finish. Thereafter the material is desirably treated with a mildly alkaline washing to remove any residual acidic material formed upon decomposition of the quaternary compound during treatment, and dried. The treatment may be followed by a single aqueous wash before drying, if desired, although this may be omitted since subsequent laundering of the treated fabric accomplishes the same purpose. The treatment may be termed a finishing treatment, since it is most usefully applied after weaving, forming, dyeing, weighting, filling or the like have been carried out. Cotton clothso treated appears to contain residual combined fluorine, indicating that at least a portion of the treating agent has reacted in some fashion, probably through the hydroxyl groups present in the fiber, although this hypothesis is not to be construed as limiting the invention.

It is a surprising feature of cotton fabric treated with these quaternary derivatives that not only is the cloth rendered oiland water-repellent but also it possesses a considerable degree of soil-resistance, that is, it does not become soiled as readily as untreated fabric. Furthermore, when soiled the fabrics thus treated are readily launderable or dry-cleaned to return them to clean condition, after which they retain their oiland water-repellency, and soil-resistance. The value of cloth so treated, for example, for childrens clothes, or for uniforms for workers around oily machinery, automotive service men and the like will be readily apparent.

The color of the fabrics treated with the compositions of the invention, and their tensile strength, are not affected by the treatment. The hand of cotton fabrics appears to be improved by the treatment.

It is noted that the finishing treatment of the invention can be applied to resin-treated, wrinkle-resistant fabrics without adversely affecting the desirable nonwrinkling feature of such fabrics.

The procedure for the preparation of the quaternized compounds of the invention, and the application of the latter to fabrics, especially cellulosic materials, are more specifically illustrated in the following examples, in which all parts are by weight and all percentages of solutions w/v. unless otherwise specified. It will be understood that these examples are illustrative only, to show the best mode presently contemplated of practicing the invention, and are not to be construed as limiting as to the scope of the invention.

EXAMPLE 1 Omega-(N-methyl) perfluorooctanesulfonamidohendecanoic acid is prepared by the procedure described in Example 4 of U.S. Patent No. 2,809,990. In that procedure, thestarting compound was N-methyl perfluoroctanesulfonamide, C8F17SO2NHCH3, of which 51.3 grams was neutralized with 2.3 grams of sodium dissolved in methanol. The solution was evaporated to dryness and 100 grams of acetone and 32.7 grams of ethylbromoundecylate, Br(CH COOC H were added. The mixture was refluxed for 18 hours, poured into ether, and the sodium bromide precipitate was filtered off. The filtrate was vacuum distilled and 55.5 grams of a out which came over at 180-185 C. (0.75 mm.) was collected. This material had a melting point of 53 C. and was the ethyl ester of the desired acid. A mixture of 40 grams thereof, 20 grams of acetic acid and 0.5 gram of concentrated sulfuric acid was refluxed for 2 /2 hours, following which the ethyl acetate and acetic acid were distilled off. The residue was poured into ether and the solution was washed with water. Evaporation of the ether yielded 35 grams of a white powder which was identified as the desired acid:

The acid thus prepared melts at 94 C.

A mixture of 135 parts of the above acid and 90 parts each of purified thionyl chloride and benzene is stirred together in a vessel equipped with reflux condenser, first at room temperature (about 20 to 25 C.) and then at 60 to 80 C. for 6 hours. The hydrogen chloride which is formed and entrained vopors are condensed in a trap cooled with solid carbon dioxide. The reaction mixture is then evaporated first at about 10 mm. Hg at 90 C. and then at about C. at less than 1 mm. Hg to remove benzene and unreacted thionyl chloride. On cooling, the light brown acid chloride corresponding to the starting acid, which remains as the residue, solidifies. The acid chloride thus prepared melts at about 9899 C.

Dry ammonia gas is passed into a stirred, externally cooled solution of 123 parts of the above-prepared acid chloride is about 1400 parts of dry diethyl ether for about 2 /2 hours until reaction appears to have ceased (a drop in temperature is noted). A precipitate of the corresponding amide forms. The reaction mixture is filtered to recover the amide and the crude product is rinsed with ether and dried. It is recrystallized from hot 95 percent ethanol. The white l1(N-methyl-perfluorooctanesulfonamido) hendecanamide thus prepared is soluble in chloroform, and insoluble in acetone or ether at room temperature.

Calculated for C2QH25F17N2SO3: C, N, 4.02%. Found: C, 34.7%; N, 3.93%.

in a vessel cooled to about 10 C. and provided with a mechaical agitator, a condenser fitted with a drying tube and a thermometer are placed 50 parts of the aboveprepared amide, 8.2 parts of pyridine hydrochloride (dried by distillation of benzene therefrom, 3 parts of parafor-maldehyde and 245 parts of pyridine. The reaction mixture is heated. Some foaming occurs at 50 C. but the reaction mixture becomes clear at 65 C. Heating with agitation is continued for five hours at 75 to C. and the mixture is then cooled to room temperature, whereupon a precipitate of the desired pyridinium chloride salt is formed, and is recovered by filtering. The solid crude product is slurried with about 320 parts of acetone, collected and dried. The dried crude product is recrystallized from acetone to provide omega-ll-(N- methylperfluorooctanesulfonamido) hendecanamidomethyl pyridinium chloride, melting at about 144149, C. All the above filtrates are combined and evaporated, and provide a further quantity of somewhat less pure material. Thisquaternized halomethyl amideis soluble in chloroform, less so in acetone and insoluble in ether. A dilute solution in water foams when shaken.

Calculated for C H F N SO Cl-H O: C, 37.1%; N, 4.99%; H O, 2.14%. Found: C, 37.0%; N, 5.2%; H 0, 2.4%.

EXAMPLE 2 When the procedure of Example 1 above is applied to produce other N-alkyl perfluoroalkanesulfonamides by forming the sodium salt of the N-alkyl perfluorosulfonamide and condensing with an alkyl omega-halo-alkanoate, other materials are obtained which can be converted to quaternized N-halomethyl amides of the invention as described in Example 1 or by the alternative and equivalent process of halomethylation and subsequent quaternization. Thus, when the sodium salt of'N-butyl-perfluorooctanesulfonamide is condensed with ethyl-beta-bromopropionate, the ester ammonolyzed, the amide bromomethylated wtih paraformaldehyde and hydrogen bromide and then quaternized with trimethylamine, there is obtained 3-(N-butylperfluorooctanesulfonamido)-propionamidomethyl trimethyl ammonium bromide. Likewise, omega (N-ethyl-perfluorobutanesulfonamido)tridecanoamide-methyl phenyl diethyl ammonium chloride and omega (N-butyl perfluorododecanesulfonamido) hexanomidomethyl tricyclohexyl ammonium bromide are produced respectively from the sodium salt of N-ethyl perfiuorobutanesulfonamide and ethyl omega-bromo-tridecanoate followed by ammonolysis, chloromethylation and quaternization with diethyl aniline and from the sodium salt of N-butyl-perfluorododecanesulfonamide and ethyl omega-bromo-caproate followed by ammonolysis, bromomethylation and quaternization with tricylohexyl amrne.

7 EXAMPLE 3 The process for production of soil-resitsant, waterand oil-repellent cloth using the quaternary ammonium compounds of this invention is carried out as follows:

The treating solution is prepared by warming sodium acetate trihydrate and the selected quaternary ammonium treating agent in water at the desired concentrations, which can range from about 0.1 to about 5 percent, at about 30 to 40 C. until solution is effected. It is to be noted that at higher concentration the solution tends to become mucilaginous, resembling a colloidal dispersion. The cloth to be treated is soaked in the solution for 1 minute, removed and squeezed so that a weight of solution approximately equal to 75 to 125 percent of the weight of the cloth is retained. Under these conditions, the preferred concentration of treating solution ranges from about 0.5 to about 2 percent. The cloth is then dried for about 10 to 30 minutes at 40 to 100 C. and the treatment is fixed by heating the cloth for about 5 to 30 minutes at from about 100 to 140 C. The fixed, treated cloth is washed for about 30 minutes in an aqueous solution containing 0.1 percent w./v. of sodium lauryl sulfate and 0.2 percent w./v. sodium carbonate, at about 50 to 60 C., rinsed thoroughly and again dried. Other alkaline agents, such as dilute alkali metal hydroxides, bicarbonates, ammonium hydroxide and the like can be used instead of alkali metal carbonates, to provide a mildly alkaline washing solution.

The effectiveness of the treatments is determined by means of tests for spray rating, oil repellency rating and visual estimation of soil repellency both before further treatment and after one or more cycles of laundering and/ or dry cleaning.

For test purposes, laundering is accomplished by washing in an automatic washing machine of the stationary tub type using a detergent under normal household procedures or by means of a standard 60-minute cycle in a Launder- O-Meter, using chip soap as specified in ASTM D-496. Dry-cleaning is performed by available commercial procedures employing, for example, perchloroethylene or naphtha.

Determination of water repellency rating is made by means of the Spray Test (Standard Test Method No. 22-52, published in the 1952 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists, vol. III, p. 136).

Oil repellency of the treated cloth is measured by a severe test in which its resistance to penetration by solutions of mineral oil in heptane is determined. (Higher proportions of heptane bring about quicker penetration.) A material wet by mineral oil alone in less than 3 minutes rates zero, if it is only wet after 3 minutes it rates 50, while resistance to penetration by a mixture of equal volumes of heptane and mineral oil rates 100. The ratings for resistance for 3 minutes are as follows.

Percent heptane: Rating 50 20 .70 30 80 40 90 50 100 60 100+ A rating of 70 or higher indicates a high degree of resistance to staining by salad oil and the like.

The 11 (N methyl) perfiuorooctanesulfonamidohendecanamidomethyl pyridinium chloride of Example 1 is applied to kierboiled standard cotton jeans cloth in 2.5 percent w./v. solution containing 1 percent of sodium acetate trihydrate as described hereinabove, drying at about 100 C. for about 30 minutes, followed by curing at 150 C. for 5 minutes.

After a mildly alkaline wash as described above, rinsing and again drying, it is subjected to tests before and after C) laundering (as described) to determine oiland waterrepellency, with the following results:

Table I Spray Rating Oil Rcpcl- Percent F lency in Fabric Before laundering 00 100+ 0.71 After laundering 100+ 0. 09

A further sample using the same fabric is prepared using a 2.5 percent solution of the treating agent and treating the cloth as set forth above. It is dry-cleaned in two successive times and tested with the following results:

Table II Spray Oil Rcpcl- Percent F Rating lcncy in Fabric Initially 0. 58 After 1 dry cleaning 80+ 100+ 0. 40 After 2 dry cleanings 80- 100+ 0. 23

0-as dark as control (untreated cloth sample) lslightly less dark than control 2-more than about half as dark as control 3less than about half as dark as control While the ratings are somewhat subjective, and may vary to a certain extent as to the degree of soil involved, it is significant that there is markedly less soiling of samples treated with the compounds of the invention and this property is retained after laundering.

The synthetic soil mixture is prepared by blending the following:

Parts by weight Peat moss 38 Portlant cement 17.0 Kaolin clay 17.0 Silica (800 mesh) 17.0 Furnace black (high leading, blue tone, powdered (Malacco)) 1.75 Red iron oxide 0.5 Mineral oil (heavy) 8.75

The blend is placed in a large pan and dried in a forced draft convection oven for 2 hours at 50 C. and then ground in a ball mill. The finely divided material which is produced is stored in a desiccator over calcium chloride or sulfuric acid.

The samples described above are rated at +3 when tested as above for soil resistance before laundering or dry cleaning and the rating is only slightly decreased after these treatments.

Further samples are treated with omega-(N-methyl)- perfluorooctanesulfonamidohendecanamidomethyl pyridinium chloride as described above using 1.4 percent of this treating agent and 1 percent sodium acetate trihydrate in water. Drying is carried out at 80 C. for 30 minutes followed by curing for 5 minutes at C. The samples are then Washed as above with a dilute aqueous alkaline solution of sodium lauryl sulfate. Samples of a nylon upholstery fabric (designated A and B) and of an 80 x 80 count cotton fabric (designated C and D) are treated as above and rated for oil and water repellency and soil resistance and then cleaned repeatedly and again rated for oil and water repellency, with the following results:

Spray rating Dryeleaned once:

Oil rating 100 Spray rating Dry-cleaned thrice Spray rating The results show that this quaternary ammonium compound is very efiective on cotton after one dry-cleaning and still exerts some effect even after three dry-cleanings. It is more resistant to laundering. It will be apparent that the treating solution containing afrorn about 1.4 to 2.5 percent of the treating agent is highly effective and that at least about 0.2 percent fluorine should be present in the treated fabric after curing to provide desirable oil, water and soil repellency after laundering. However, it is found that a solution containing 1.0 percent is also very effective and that as loW as 0.1 percent concentration can be used to treat fabrics, which then show excellent oil, Water and soil repellency before laundering. When the quaternized N-halomethyl amides of Example 2 are employed to treat cotton fabrics under the conditions of concentration, time and temperature set forth above, substantially the same results are obtained. Likewise treatment of wool, nylon and rayon fabrics by the above procedure confers oiland Water-repellency thereon.

The solutions used for treating fabrics as set forth above can also be applied to paper with slight modifications in procedure to avoid damaging the structure of the paper, which, as is well known, is weakened by treatment with Water. Thus, the excess of treating solution is removed by permitting the paper to drip dry or by running the Web between rolls, while drying and fixing are accomplished by heating the individual sheets or by hot-roll calendering long strips or continuous rolls. The treated paper is oiland water-repellent. The surface of wood is rendered repellent to oil and water and resistant to soiling by treatment with the above solutions painted on, heated and subsequently neutralized and dried.

EXAMPLE 4 This example illustrates the use of the compositions of this invention in conjunction with chemically compatible treating agents which can be employed either to produce a multiplicity of results or a synergistic combination of results. Such effects may be sought where increased resistance to water is sought, even at slight expense of the oil repellency, or where both will be somewhat sacrificed to impart additionally, for example, crease, crush or wrinkle resistance.

Thus, when untreated samples of 80 X 80 count cotton cloth are treated as above with a 1 percent aqueous solution of the pyridinium chloride of Example 1 containing additionally about perecnt of a melamine-formaldehyde condensate of the type used for imparting Wrinkle resistance, about 1 percent of an accelerator to advance the cure of the resin and 1 percent of sodium acetate trihydrate, dried for 10 minutes at 80 C. and cured for 5 minutes at 150 C., then rinsed with a solution of an ammonium soap and cured for a further 6 minutes at 150 C., the samples shown no noticeable discoloration and show both oiland water-repellency as Well as soilresistance. The repellency is slightly reduced by 3 laun- 10 derings but soil-resistance is retained. The crease-resistance conferred by the other additives is still evident.

Substantially the same results are obtained when the crease resistance promoting treatment is applied first and the dried cloth is subsequently treated with a 1 percent aqueous solution of the pyridinium chloride of Example 1 containing about 1 percent of sodium acetate trihydrate and cured and Washed as described above. It is thus apparent that the quaternized N-(halomethyl)amides of the invention can be used concurrently or sequentially with other treatments available in the art.

When samples of cotton jeans cloth are treated in duplicate with the agent of Example 1 above with and Without the addition of an N-alkylstearoamidomethyl pyridinium chloride representative of commercially accepted agents for imparting temporary water-repellency to cotton, it is found that there is slight reduction in oil-repellency and increase in water-repellency in the sample treated with the combination of agents.

What is claimed is:

1. A compound of the formula:

0 RtsO2l l(CH iNHOHzQ+X-' wherein R is perfluoroalkyl having 4 to 12 carbon atoms, In is an integer from 2 to 12, R is a member of the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms, Q is a tertiary nitrogenous organic residue selected from the group consisting of trialkylamino having 3 to about 36 carbon atoms, tricycloalkylamino having about 18 carbon atoms, aralkylamino having about 8 carbon atoms, arylamino having about 8 carbon atoms, pyridino, picolino, lutidino and quinolino, and X is a halogen of the group consisting of chlorine and bromine.

2. Omega (N methyl) 11 perfiuorooctanesulfonamidohendecanamidomethyl pyridinium chloride.

3. The process for rendering fibrous materials Waterand oil-repellent, which comprises treating thefibrous material with a compound of the formula:

wherein R is perfiuoroalkyl having 4 to 12 carbon atoms, In is an integer from 2 to 12, R is a member of the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms, Q is a tertiary nitrogenous organic residue selected from the group consisting of trialkylamino having 3 to about 36 carbon atoms, tricycloalkylamino having about 18 carbon atoms, aralkylamino having about 8 carbon atoms, arylamino having about 8 carbon atoms, pyridino, picolino, lutidino and quinolino, and X is a halogen of the group consisting of chlorine and bromine; in aqueous medium bufitered to about pH 5.5 to 6.5, drying the treated fibrous material and heating the dried, treated material to a temperature in the range of about C. to C. for about 5 to 30 minutes.

4. A fabric finished with a compound of the formula:

wherein R is perfluoroalkyl having 4 to 12 carbon atoms, In is an integer from 2 to 12, R is a member of the group consisting of hydrogen and alkyl having from 1 to 6 carbon atoms, Q is a tertiary nitrogenous organic residue selected from the group consisting of trialkylamino having 3 to about 36 carbon atoms, tricycloalkylamino having about 18 carbon atoms, aralkylamino having about 8 carbon atoms, arylamino having about 8 carbon atoms, pyridino, picolino, lutidino and quinolino, and X is a halogen of the group consisting of chlorine and bromine; whereby the fabric contains residual combined fluorine and has oiland water-repellent properties.

5. A cellulosic fabric having oiland Water-repellent properties together with soil resistance and good hand,

1 1 finished with omega-(N-methyD-ll perfluorooctanesul- 2,233,296 fonamidohendecanamidomethyl pyridinium chloride. 2,292,997 2,412,054 References Cited in the file of this patent 2,809,990

UNITED STATES PATENTS 5 2,146,392 Baldwin et a1 Feb. 7, 1939 2,216,406 Austin Oct. 1, 1940 12 Nelles Feb. 25, 1941 Hentrich Aug. 11, 1942 McClellan Dec. 3, 1946 Brown et a1 Oct 15, 1957 OTHER REFERENCES Noller: Chemistry of Organic Compounds, 2nd edition, page 241 (Saunders) (1957).

Claims

1. A COMPOUND OF THE FORMULA:

5. A CELLULOSIC FABRIC HAVINGN OIL- AND WATER-REPELLENT PROPERTIES TOGETHER WITTH SOIL RESISTANCE AND GOOD HAND, FINISHED WITTH OMEGA-(N-METHYL)-11-PERFLUOROOCTANESULFONAMIDOHENDECANAMIDOMETHYL PYRIDINIUMCHLORIDE.