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Publication numberUS3510494 A
Publication typeGrant
Publication dateMay 5, 1970
Filing dateMay 17, 1966
Priority dateAug 12, 1963
Also published asDE1469290A1
Publication numberUS 3510494 A, US 3510494A, US-A-3510494, US3510494 A, US3510494A
InventorsDomenick Donald Gagliardi
Original AssigneeColgate Palmolive Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Certain perfluoro alkanamido-,perfluoro alkanoyloxy-,perfluoroalkyloxy and perfluoro mercapto - quaternary ammonium compounds,the corresponding pyridinium compounds and derivatives thereof
US 3510494 A
Abstract  available in
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Description  (OCR text may contain errors)


signor to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Continuation-in-part of application Ser. No. 301,628, Aug. 12, 1963. This application May 17, 1966, Ser. No. 550,646 7 Int. Cl. C07d 31/32, 87/42; C07c 87/30 US. Cl. 260-295 p 10 Claims ABSTRACT OF THE DISCLOSURE Highly fluorinated quaternary ammonium compounds containing between the fiuoro moiety and the quaternized nitrogen one of three linkages selected from the group which represent carboxamido, thioether and acid groups respectively are provided which are outstanding for producing water repellent, oil repellent and soil repellent finishes on textiles as well as resistance to staining.

The present invention is a continuation-in-part Ser. No. 301,628 now abandoned, filed Aug. 12, 1963, and relates to soil-proofing textiles and to the soil-proofing quaternary ammonium compounds used and, more'particularly to soil-proofing textiles with perfluoro quaternary ammonium compounds and to the perfluoro quaternary ammonium compounds per se.

For centuries man has sought to alleviate the discomfort concomittant with exposure to rain. It was not until about 1935 that there was any attempt to discover the factors controlling resistance to wetting by water. Prior to this time, textile materials were coated fabrics with various cookbook recipes such as rubber, linseed oil-rubber mixtures, empirical and whimsical synthetic dopes and other compositions having no basis in a discovery of the physical properties of a preparation which would impart to a textile the capability of water-repellency.

A large variety of such products are still in use as lowcost, non-durable water repellents for textiles. Since neither thermosetting nor fiber reaction occurs when textiles are coated with such products, the treated textile is nondurable to washing and dry cleaning. Other than water repellency for rainwear fabrics, such mixtures provide fabrics with a fair degree of spot and stain resistance to water-borne chromophoric materials.

The search for durable or permanent water repellents as contrasted with these non-durable water repellents, especially for cellulosic fibers was initiated by the need to overcome the deficiencies of these wax emulsion-metallic salt mixtures.

While durable water repellents had been initially developed for outerwear and raincoat applications, it was soon recognized that durable Water repellents could be used as finishes for other purposes. In the period 1950 to 1956 these durable water repellent finishes were Widely used on mens suitings, dress goods, and upholstery materials. When ofiering these products to the textile finishing trade, promotional emphasis was not placed on waterrepellency but on spot-and-stain resistance. This use has continued to the present time. It had been observed that fabrics treated with such durable water repellents had a high degree of resistance to soiling by water-borne soils and stains and were easier to launder. The primary limitation of these finishes was that they attracted rather than repelled oily soils, and the treated fabrics were not resistant to staining by oily materials such as oils, greases, gravy, mayonnaise, etc. a

Although fabric finishes capable of-providing waterand-oil repellency and resistance to staining by Water-andoil borne stains are important for wearing apparel, upholstery and the like, the capability of resisting staining by oily particulate soil is of greater importance for aesthetic, if for no other reasons. That is to say, the finely divided environmental grime mixed with the oil exudations of the human skin, i.e., oily particulate soil, soil in the neckband and cuffs of a mans shirt, are far more often encountered than soiling with gravy or mayonnaise.

It has now been discovered that chlorine resistant fluoroquaternary ammonium compounds having compositions corresponding to the following formula provide textiles with water-repellency, oil-repellency, resistance to staining by water-borne and oil-borne stains and the ability to shed dry soil:

Where X is R, R" and R' are alkyl groups having 1 to 6 carbon atoms of which two adjacent carbon atoms can form with the nitrogen a heterocyclic group having 5 or 6 carbon atoms or aromatic groups. R, R" and R can be the same or different, e.g., two or R, R and R' can be alkyl or cyclo-alkyl groups and the other can be an aromatic group; Q is an alkyl, aryl, alkyl-aryl or cyclo-alkyl radical having three to twenty-one carbon atoms and 7 to 43 hydrogen atoms of which hydrogen atoms 70 to percent are replaced by fluorine atoms and the terminal carbon group preferably has three fluorine atoms attached thereto; and R is alkyl, hydroxyalkyl, aryl, haloalkyl, or haloaryl.

As used herein, the term chlorine resistant refers to the ability of the compound on the fabric, after bleaching with chlorine, to resist yellowing and fabric damage which normally occurs when fabric treated with non-chlorine resistant fiuoro-quaternary compound is bleached during laundering and then is ironed.

The term textiles as used herein refers to fibers, yarns, woven fabrics, felted materials composed in part or in whole of cellulosic material such as cotton, synthetic cellulosic material such as regenerated cellulose, proteinaceous material such as wool or synthetic fibers such as nylon, fiberglass, acrylic, polyester fibers and non-woven fabrics. In addition, solid materials such aspaper, wood, leather and the like may also be treated where it is desired to impart oil, water or any soil repellency.

The quaternary ammonium compounds are made by the classical methods of organic chemistry. The methods of preparation of these quaternary ammonium compounds form no part of the present invention. Hence, the preparation of these quaternary ammonium compounds need not be described in detail. It suffices to describe the preparation of N-hydromethyl-perfluorooctanamidomethyl pyridinium acetate as illustrative of the preparation of these quaternary ammonium compounds corresponding to the formula:

having compositions Theperfluoroalkanoic acid amide can then be converted to N-alkyl, perfluorooctanamidomethyl pyridinium acetate by reaction with pyridine and paraformaldehyde in glacial acetic acid. This reaction can be considered to be represented by the Equation 2:

CF3(CF2)5CONH2 C NH CHZO CHQCOOH The perfiuorooctanamidomethyl pyridinium acetate is then made chlorine resistant by reacting it with formaldehyde. The reaction can be represented by Equation 3:

Thus, 0.1 mol of pentadecafluorooctanamide, 0.15 mol of pyridine, 0.15 mol of 91 percent paraformaldehyde and fifty'parts by weight of glacial acetic acid were charged to a three neck flask having a stirrer and a condenser. The contents of the flask were heated to 112 C. After about thirty minutes at 112 C. all of the paraformaldehyde had'dissolved to yield a clear yellow solution. After an additional nineteen and one-half hours at a temperature in the range of 112 C. to 126 C., the reaction mixture was cooled to room temperature. The reaction product settled out and was recovered. The reaction product was reacted with one mol equivalent of formaldehyde to make it chlorine resistant.

The prior art perfluoro-quaternary ammonium compounds described in US. Pat. No. 2,727,923 (Formula C) and US. Pat. No. 3,147,065 (Formula D) are not to be confused with the chlorine resistant fiuoro-quaternary ammonium salts of this invention (Formula E):

Where n has an integer value of 3 to 9 and the Rs are alkyl groups (which can be the same or different) that contain 1 to 5 carbon atoms.

wherein X is chlorine or bromine; R is a divalent radical selected from the group consisting of 4 and m is an integerfrom l to 10; and Ii is an integer from 3 to 12.

where n has an integer value of 3 to 21 even when R", R" and R' are the same as R, R and R in Formula C, and R, R", R, R and X having the meaning set forth in FormulaB.

The quaternarysammonium compounds of the present invention react with the active hydrogen in the surface of the substrate even at low temperatures, e.g., 300 F. and lower and are substrateor fiber-reactive. In addition, the quaternary ammonium compounds of the present invention endow the substrates to which they are aflixed with water repellency when the number of carbon atoms in Q in the formula is at least three. Furthermore, the quaternary ammonium compounds of the present invention have the highly desirable property of being chlorine resistant so that substrates to which they are afiixed, in addition to being provided with water, oil and soil repellency properties, and are highly resistant during and after laundering, bleaching and ironing to yellowing and fabric damage.

By employing other starting materials, it is possible to readily prepare other compounds of the invention. Thus, one mol equivalent of C fluoroalcohol reacted with one mole equivalent of paraformaldehyde and one equivalent of morpholine when dissolved in xylene and heated to azeotrope off the water to yield a reaction product which, after the xylene is removed by vacuum stripping, then reacted with one mole equivalent of benzylchloride for about 3 hours, will yield another compound of the present invention. The product obtained is solid, is dispersible in hot water and when applied to textiles, provides desirable repellencies. The reaction can be represented by Equations 4 and 5:

produces satisfactory oil repellency. The reaction can be represented by Equation 6:

(6) C F COOH CHzO HBCCOOH NC H Another product may be obtained by reacting one mol equivalent of perfluorooctyl mercaptan and one mol equivalent of paraformaldehyde in an excess of benzene by passing dry HCl gas into the mixture until the paraformaldehyde disappears. The water is the azeotroped oil and an intermediate product is obtained which when reacted with one 'mol equivalent of triethylamine provides an exothermic reaction. The reaction is heated until the theoretical chloride content has formed and the Yet another product may be obtained by mixing one mole of pentadecafluorooctyl alcohol with one mole of p-hydroxy benzoic acid in toluene, sodium methoxide is added as a catalyst and the mixture is heated to reflux temperature. Reflux is continued using an azeotropic separator to remove water as it is formed during esterification:

C1FrsCH2OH Hooc 3orr1 When the reaction is completed, one mole of paraformaldehyde is added to the solution. Then HCl gas is bubbled through the solution until the paraformaldehyde dissolves and the chloromethyl ether of perfiuorooctyl phenol ester has formed:

C7F15CH2O 0060 CHzCl are The solution is cooled and one mole of triethyl amine is added slowly to form the fluorinated quaternary. This crystallizes out of solution as it is formed:

The resulting product is filtered, 'washed with cold alcohol and dried. When applied to textiles at 0.5-3 .0% concentration it produces water, oil and soil repellency.

Still another product may be obtained by mixing one mole of perfluorobenzamide with one mole of paraformal- 4.5 dehyde and one mole of morpholine in xylol solution. The mixture is refluxed and water collected in an azeotropic separator. After 18 grams of water are collected, the solution is cooled to room temperature:

CHzCHz C Fr-CONH2 CHzO HN /O CH2CH2 l omorn CgF5-OONHCH2N O H2O When applied to fabrics and cured at 300 F. for 5 minutes, this produces a. soil retardant finish.

The effectiveness of the treatments is determined by means of the following tests:

WATER REPELLENCY (Resistance to wetting (spray test), AATCC standard test method 22-1952) This test is applicable to any textile fabric. It measures the resistance of fabrics to wetting by a water spray and the results depend primarily on the degree of hydrophobicity inherent in the fibers and yarns and subsequent treatments to which the fabric is subjected. Water is sprayed against the taut surface of a test specimen. Evaluation of the wetted pattern is readily brought about by comparing the wetted pattern with standard wetting pattern pictures:

Rating: Characterized by- No sticking or wetting of the upper surface.

90 Slight random sticking or Wetting of the upper surface.

80 Wetting of the upper surface at spray points.

70 Partial wetting of the whole of the upper surface.

50 Complete wetting of the whole of the upper surface.

0 Complete wetting of the whole of the upper and the lower surfaces.

The test specimens of minimum size of 7" x 7" (seven inches by seven inches) are conditioned at 70 F. and 65 percent relative humidity for a minimum of four hours before testing.

The test specimen, fastened securely and wrinkle-free in a metal hoop having a diameter of 6 inches, is placed and centered 6 inches under a standard spray nozzle at an angle of 45 to the horizontal. Two hundred and fifty milliliters of water at 80i2 F. is poured into a funnel attached above the spray nozzle. The spray lasts 25 to 30 seconds at the end of which time the loop is taken by one edge and the opposite edge tapped smartly once against a solid object with the wet side facing the solid; this procedure is repeated with the hoop reversed OIL REPELLENCY (3M Textile Chemicals" Appendix ATest Methods, page 1) The Minnesota Mining oil repellency test is based on the different penetrating properties of the two hydrocarbon liquids, mineral oil (Nujol) and n-heptane. (Nujol is the tradename for white mineral or parafiin number corresponding to that mixture containing the oil being a mixture of hydro-carbons having a density for light oil in the range of 0.83 to 0.860 and for heavy oil in the range of 0.875 to 0.905.) The Nujol-heptane proportions for each rating Were selected by 3M to give oily stain resistance somewhat comparable to the waterborne stain resistance corresponding to each of the spray ratings of the AATCC Standard Test Method 22-1952.

Percent heptane (by volume) Percent Nujo I No hold out to Nujol. Percent The standard oil-heptane mixtures are contained in small stoppered medicine-dropper bottles. A drop of each mixture of Nujol and heptane is placed on the fabric. The appearance of the test oil is observed through the drop. Note is made whether wetting or penetration occurs. The

number corresponding to that mixture containing the highest percentage of heptane which does not penetrate or wet the fabric after three minutes is considered the oil repellency rating of the system.

The change in the optical refractivity of the drop is often an indication of wetting. In some cases wetting can be better determined by observing the other side of the fabric. In some cases reported hereinafter the term has been used to indicate a modicum of resistance to wetting by oil.

STAIN REPELLENCY The following procedures have been used to establish the degree of resistance to staining by water-borne and oil-borne stains of fabrics.

(a) The fabrics were stretched lightly on 12" x 31" frames. All or part of the frame was used depending upon the amount of fabric available. The frames were supported at both ends with the fabric about 8 inches above a black surface. The fabric touched nothing.

(b) 'Ihree inch medicine droppers were used to draw the stains from the containers. A 1 cubic centimeter calibration was established and marked on the exterior of each dropper. The stains were squeezed vertically downward from a height 2 inches above the cloth.

(c) After five minutes the unabsorbed stain was wiped off the fabric with two sweeps of Kleenex and the stains rated as follows:

Appearance: Rating No stain visible Slight stain 4 Easily noticeable stain 3 Considerable stain 2 Very heavily stained 1 Water stains:

(1) Instant tea 1 (2) Sheaffers 232 blue-black skrip (3) A & P Concord grape juice (4) Ann Page salad mustard (5) Bosco chocolate syrup Oil stains:

(6) Wesson oil (7) Gulf Supreme motor oil 20/20 (8) Oleomargarine 2 (9) La Rosa tomato sauce (10) Iergens lotion 8 cc. dry powder/200 cc. water applied at 160 F. 2 Melted and applied at 160 F,

In reporting the relative resistance to staining and ease of stain removal in laundering, the staining values for water-borne and oil-borne stains were averaged separately.

In all cases the stains were allowed to dry on the fabrics for twenty-four hours before laundering.

No ol'ficial test has been recognized to soil and testhousehold articles and the effect of various treatments but it has been found that the procedure given below employing a standard synthetic dry soil described hereinafter provides comparable results for the testing of dry soil repellency.

Fifteen to twenty 6"x8" size specimens (normally.

80x 80 cotton), including at least one untreated control, were tumbled for 30 minutes with 10% soil based on weight of the fabric. I

The soil was prepared by the method described by Salisbury et al. in an article entitled Soil Resistant Treatment 8 of Fabrics, American Dyestuif Reporter, Mar. 26, 1956, page 199. The soil had the following compostion:

Material: Percent by weight Peat moss 38 Cement 17 Kaolin clay, peerless (R. T. Vanderbilt) 17 Silica 200 mesh (Davidson Chem.) 17

Molacco furnace black (Benny & Smith Co.) 1.75 Red iron oxide (C. K. Williams Co.) 0.50 Mineral oil 8.75

The dry ingredients were blended thoroughly, dried in a forced draft convection oven for 8 hours at 50 C., then milled 25 hours with ceramic balls and stored in a polyethylene bag.

The tumbling was carried out in a 5 liter capacity Five Minute Homer Cleaner at 44 r.p.m.; six No. 8 neoprene rubber stoppers were distributed among the specimens to increase mechanical action. At the end of tumbling, the specimens were removed and each shaken up and down 15 times by hand to remove surface dirt.

The specimens were then cut in two to produce two 4" x 6" pieces. One half was laundered with 50 grams of a commercial detergent in a cotton cycle with a 5 pound load in an automatic home washing machine, then hung to dry and lightly ironed under a clean cotton cloth.

Since the perfluoro-quaternary ammonium compounds of the present invention are soluble in water, it is preferred to alfix the compound to the substrate from an aqueous solution of the quaternary ammonium compound. Thus, the substrate particularly a substrate having active hydrogen in the surface thereof, e.g., cellulose, wool, silk and in general natural or synthetic proteinaceous materials, nylon, etc. is immersed in a solution containing 0.2 to 3 percent of the perfluoro quaternary ammonium compound, present usually as a salt of acetic acid, hydrochloric acid, and the like, separated from the aqueous solution, wrung to to 100 percent wet pick-up, dried and preferably heat treated at an elevated temperature for a time inversely proportioned to temperature in the range of 250 to 350 F., e.g., for five to ten minutes at 300 F. In this manner about 0.15 to 3 percent of the perfluoro quaternary compound can be affixed to the textile substrate. A

Illustrative of the reaction between a substrate having active hydrogen in the surface'and the present perfluoro quaternary compound is the reaction with the active hydrogen of a hydroxyl group of cellulose ZOH where Z is the cellulose radical and OH is a hydroxyl group.

where Q has the same significance Formula E supra.

Illustrative of the resistance to soiling by water, oil, water-borne, and oil-borne materials are the following data obtained when treating cotton with pentadecafluorooctanamidomethyl pyridinium acetate.

Average stain ratings Repellency+ Percent o 11 Water-borne Oil-borne quaternary in solution B B A B A vention provides novel perfiuoro quaternary ammonium compounds which are reactive with active hydrogen in the surface of a substrate having active hydrogen to produce a coated fiber or fabric or in general a coated textile in which at least a portion of the coating is attached to the substrate by chemical bonds. Consequently, these novel quaternary compounds provide substantive coatings for textiles having active hydrogen in the surfaces thereof. Such coatings moreover do not form chloramides when bleached with chlorine and do not yellow or degrade the fibers. In addition, the compounds of the invention as previously stated can also be used to treat materials not having active hydrogen in the surface.

While the present invention has been described by means of the foregoing examples, it is to be understood that the invention is not limited thereto, reference being bad to the claims for a definition of the scope of the invention.

What is claimed is:

1. A water-soluble, chlorine-resistant fluoro-quaternary ammonium compound of the formula R [QXOH2NR" ]AN- 11 i X is -CN; S; or (JO 4 (2) R, R" and R are each alkyl radicals of 1 to 6 carbon atoms, or two of said radicals together with the nitrogen form morpholine with the proviso that when two of said terms R, R and R' represent morpholine the term X represents where:

3. A water-soluble chlorine resistant fluoro-quarternary ammonium compound as set forth in claim 1 wherein Q is pentadecafluorooctanyl.

4. A water-soluble chlorine resistant fluoro-quarternary ammonium compound as set forth in claim 1 wherein R and R" and R are pyridine.

5. A Water-soluble chlorine resistant fluoro-quarternary ammonium compound as set forth in claim 1 wherein the compound is N lower alkyl, perfiuorooctanamidomethyl pyridinium acetate.

6. A Water-soluble chlorine resistant fluoro-quarternary ammonium compound as set forth in claim 1 wherein the compound is a perfluorooctanamidomethyl pyridinium salt of an acid selected from the group consisting of acetic, hydrochloric sulfuric and nitric.

7. A water-soluble, chlorine-resistant fiuoro-quaternary ammonium compound as set forth in claim 1 wherein R and R" together with the nitrogen form a morpholine ring and R is ethyl.

8. A water-soluble, chlorine-resistant fluoro-quaternary ammonium compound as set forth in claim 7 wherein Xis 9. A water-soluble chlorine-resistant fiuoro-quaternary ammonium compound as set forth in claim 1 wherein the compound is N-(pentadecafluoroctyl thiomethyl) triethyl ammonium chloride.

10. A water-soluble chlorine-resistant fluoro-quaternary ammonium compound as set forth in claim 1 wherein the compound is N-(pentadecafluoroctanoyloxymethyl) pyridinium acetate.

References Cited UNITED STATES PATENTS 2,623,902 3/1950 Crossley 260567.6 3,147,065 9/1964 Koshar et a1. 8-116.2 3,171,861 3/1965 Ahlbrecht 260567.6 3,420,840 1/1969 Tesoro et al. 260296 HENRY R. JILES, Primary Examiner A. L. ROTMAN, Assistant Examiner US. Cl. X.R.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2623902 *Mar 15, 1950Dec 30, 1952Sharp & Dohme IncBis-quaternary ammonium salts
US3147065 *May 2, 1960Sep 1, 1964Minnesota Mining & MfgQuaternized halomethylamides
US3171861 *Dec 26, 1962Mar 2, 1965Minnesota Mining & MfgFluorinated aliphatic alcohols
US3420840 *Aug 4, 1960Jan 7, 1969Stevens & Co Inc J PFluorinated compounds
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3759981 *May 20, 1971Sep 18, 1973Pennwalt CorpEsters of perfluoroalkyl terminated alkylene thioalkanoic acids
US4049668 *Mar 21, 1975Sep 20, 1977Diamond Shamrock CorporationCationic fluorochemical surfactants
US4183367 *Nov 21, 1977Jan 15, 1980American Cyanamid CompanyEnhancing the drying of hair by the use of fluorinated catonic and amphoteric surfactants
US4859349 *Oct 9, 1987Aug 22, 1989Ciba-Geigy CorporationPolysaccharide/perfluoroalkyl complexes
US5066672 *Dec 27, 1989Nov 19, 1991Societe AtochemPolyfluoroalkyl acetates, thioacetates and acetamides, and their applications
US5525261 *Oct 18, 1994Jun 11, 1996Henkel CorporationAnti-static composition and method of making the same
EP0376801A2 *Dec 19, 1989Jul 4, 1990Elf Atochem S.A.Polyfluoroalkyl-substituted acetates, thioacetates and acetamides, their preparation and uses
U.S. Classification546/336, 564/282, 554/91, 554/52, 544/171, 544/158, 544/169, 560/65, 544/177, 554/46, 564/291, 560/110, 554/103, 564/209, 544/165, 560/227, 544/168, 564/285, 554/110, 8/188, 560/42, 564/281, 560/67, 564/292
International ClassificationB01F17/34, D06M13/408, D06M13/322, C07D295/13
Cooperative ClassificationC07D295/13, D06M13/408, D06M13/322, D06M13/46
European ClassificationD06M13/322, D06M13/408, C07D295/13