US3564029A - Hydroxymethylated,fluoroacylated aminohydroxy aromatic compounds - Google Patents

Abstract

PERFLUOROACYLKAMINOHYDROXY AROMATIC COMPOUNDS ARE PROVIDED WHICH ARE OUTSTANDING FOR PRODUCING OIL AND WATER REPELLENT EFFECTS ON TEXTILES AS WELL AS INCREASING THE RESISTANCE TO SOILING BY OILY PARTICULATE SOIL. THE AROMATIC NUCLEUS WHICH MAY CONTAIN 1,2 OR 3 RINGS MAY CONTAIN 1 OR 2 AMINO GROUPS, 1 OR 2 HYDROXY GROUPS AND UP TO 2 HYDROXY METHYL GROUPS. ONE OR 2 OF THE AMINO GROUPS ARE ACYLATED WITH A PERFLUORO ACYL GROUP CONTAINING FROM 3 TO 21 CARBON ATOMS IN WHICH AT LEAST 70% OF THE HYDROGENS HAVE BEEN REPLACED WITH FLUORINE. THE COMPOUNDS MAY ALSO CONTAIN ALKYL SUBSTITUENTS OF FROM 1 TO 5 CARBON ATOMS.

Description

United States Patent 3,564,029 HYDROXYMETHYLATED, FLUOROACYLATED AMINOHYDROXY AROMATIC COMPOUNDS Domenick Donald Gagliardi, East Greenwich, R.I., as-

signor to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Nov. 7, 1967, Ser. No. 681,084 Int. C]. (1091: 7/00 U.S. Cl. 260-404 8 Claims ABSTRACT OF THE DISCLOSURE Perfluoroacylaminohydroxy aromatic compounds are provided which are outstanding for producing oil and water repellent effects on textiles as well as increasing the resistance to soiling by oily particulate soil. The aromatic nucleus which may contain 1, 2 or 3 rings may contain 1 or 2 amino groups, 1 or 2 hydroxy groups and up to 2 hydroxy methyl groups. One or 2 of the amino groups are acylated with a perfluoro acyl group containing from 3 to 21 carbon atoms in which at least 70% of the hydrogens have been replaced with fluorine. The compounds may also contain alkyl substituents of from 1 to 5 carbon atoms.

lysts and to solid substrates having attached thereto the polymers produced by alkaline catalysis of a monomer of hydroxymethylated fluoroacylated aminohydroxy aromatic compound.

While man has used woven textiles for raiment for more than two thousand years, it was not until about one hundred years ago that he sought to make woven textiles water repellent. The first and, in the light of recent knowledge of the basic principles of surface free energy, contact angle and spreading coefficient, unsophisticated water-proofing agents were various mixtures compounded according to cookbook recipes which, when applied to woven textiles, coated the surface and filled the interstices of the woven fabric with air-impervious and water-repellent material. This served to provide rainwear such as the Macintosh and the souwester but was not completely satisfactory for other uses.

In the period 1935 to 1940 in Germany especially at Chemische Fabricke Pferze with an empirical approach and without understanding the basic principles of water repellency, a series of wax emulsions was developed which, when padded onto textiles, produced a high contact angle of water drops on the surface of the textile and a high degree of shower resistance without changing the porosity or air permeability of the textile material. The fabrics so treated were not wettable by water or by waterborne stains because of the change in free energy of the fiber surfaces and not because, as in prior art treatments of closing the interstices of the fabric with deposits of treating material. By the use of the new wax emulsionmetallic salts compositions, it became possible to produce fabrics which had the feel and appearance of conventional untreated fabrics but did not look like oil-cloths, or rubberized coated fabrics. The primary practical limitation Patented Feb. 16, 1971 of such compositions was and still is the lack of durability to washing and dry cleaning. Products of this type generally comprise a composition containing (a) a parafiin wax or mixtures of vegetable wax esters such as Carnauba, Candelilla, or Sugar Cane Wax; (b) an emulsifying agent, generally glue, gelatin, and rosin soaps; and (c) an aluminum or zirconium salt, usually the formate or acetate. The primary function of the salt is to insolubilize the glue and other emulsifiers after the emulsion is deposited on the fabric.

A large variety of such products are still used as lowcost, non-durable water repellents for textiles. Since neither thermosetting nor fiber reaction occurs with such products, they all are non-durable to washing and dry cleaning. Other than water repellency for rainwear fabrics, such products produce fabrics which have a fair degree of spot-and-stain resistance to water-borne stains.

The search for durable or permanent water-repellent finishing materials especially for cellulosic fibers was initiated because of the deficiencies of the afore-discussed wax emulsions. The first major improved product was offered in England under the trade name of Velan. Velan was octadecyloxymethyl pyridinium chloride, a quaternary ammonium compound made by the chloromethylation of octadecanol followed by quaternization with pyridine and having a composition corresponding to the formula:

H H 0:0 0 123E310 0 H2111:

\OC Cl'H E This structure, unlike other quaternary ammonium compounds, is unstable and under acid conditions reacts with surfaces containing active hydrogen, e.g., the hydrogen of a hydroxyl group in cellulose fibers. If Z be the core of the cellulose fiber and OH be an hydroxyl group in the surface thereof, then the reaction can be represented by the formula:

011E350 ONHCHQIE C which is available commercially as Zelan and Norane R. The advantage of the stearamide product is greater initial water repellency and greater durability to washing. Such products are leaders in rainwear fabric finishes.

In the search for other fiber reactive or durable water repellents, other classes of materials have now evolved as represented by silicone water repellents, methylol stearamide compositions (Permel, Ahcovel NW), hydrophobic resins (Norane GG, Ranedare R, Argus DWR), octadecylketene dimer (Aquapel), and others.

While durable water-repellent finishes had been initially developed for outerwearand rainwear-type applications, in the period 1950 to 1956 such products began to be used widely on mens suitings, dress goods, and upholstery materials. In this exploitation of these finishes emphasis was placed not on water repellency but on resistance to spotting and staining by water-borne stains. This use continues. 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 principal limitation of such finishes was that they attracted rather than repelled oily soils and the fabrics were not repellent to staining by oil materials such as oils, greases, gravy, mayonnaise, etc.

In the early part of the decade of 1950 to 1960 based on work done at the Naval Research Laboratory by Fox and Zisman and work done by the Kellogg division, later to become a part of the operations of Minnesota Mining and Manufacturing Company, the latter announced the utility of certain fluorocarbon based chemicals as finishes for various fibers. Fox and Zisman had demonstrated the physiochemical principle of low free-energy surfaces and the relation to non-wetting with water and oil of surfaces treated with chemicals containing perfiuoroalkyl groups.

The practical developments of Minnesota Mining and Manufacturing Company resulted in the first product directed to textile finishing. This was and still is the product known as FC-l49. FC-l49 is a classical Werner complex of a carboxylic acid made by reacting one mol of the carboxylic acid with 2 mols of basic chromic chloride to obtain a reaction product having a composition represented by the formula:

The compound is water soluble and cationic in nature. It shows strong adhesion to anionic substrates such cellulose and Fiberglas. It also complexes with proteinaceous materials such as wool, silk, and leather to yield both waterand oil-repellent surfaces.

A second general class of products developed by Minnesota Mining and Manufacturnig Company (often referred to as 3M) comprise latices of perfluorochemicals. For example, some of these are believed to have a composition corresponding to the formulae:

These various products made available by 3M" produced a great practical improvement in fabric finishes. Although of some merit for plain water repellency for outerwear finishing, the two products offered a solution to obtaining water and oil repellency and practical resistance to staining. Because of its hydrolytic instability, the Werner complex product has been limited to wool, leather, and upholstery finishes. The aciylate products have become prominent in finishing cotton, rayon, and synthetic fibers.

Thus, while the progress in the art of imparting waterrepellency to textiles has been noteworthy, the soiling problem has not been solved. Recognizing the need for reproducible results, those concerned with research in this field have developed a test for water repellency, a test for oil repellency, a test for resistance to water-borne and oil borne stains and, for houshold furnishings, the most important: a test to evaluate particulate soil repellency.

WATER REPELLENCY Resistance to Wetting (Spray Test) AATCC Standard Test Method 22-1952 This test method 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 applied. 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: Appearance of test specimen 100 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 the spray points.

70 Partial wetting of the whole of the upper surface.

Complete wetting of the whole of the upper surface.

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

When measuring the spray rating, especially of finishes of the present invention, it is not unusual to encounter a test specimen with sufficient hydrophobic properties to confine the area of wetting and yet permit wetting through. Thus, it becomes necessary to have a rating for this condition. The following illustrates this modification of the standard wetting evaluation:

A spray rating number of /0 is reported for a spray pattern comparable to the standard 70 rating but the undersurface is also wetted to some extent. The 70 of the numerator indicates equivalence with the standard test pattern for a rating of 70. The zero in the denominator indicates wetting to the undersurface of the cloth at the Wet areas.

The test specimens having a minimum size of 7" x 7" 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 degrees to the horizontal. Two hundred and fifty milliliters of water at i2 F. is poured into the funnel attached above the spray nozzle. The spray lasts twenty-five to thirty seconds at the end of which time the hoop 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 degrees.

OIL REPELLENCY TEST 3M Oil Repellency Test: "3M Textile Chemicals (Appendix A, Test Methods, page 1) The Minnesota Mining and Manufacturing Company oil repellency test is based upon the different penetrating properties of the two hydrocarbon liquids, mineral oil tNujol") and n-heptane. The Nujol-heptane proportions for each rating were selected by 3M so as to give oily stain resistant somewhat comparable to the waterborne stain resistance corresponding to each of the spray Percent y volume Percent heptare,

y volume Oil repellency rating 1 No hold out to Nujoli The standard oil-heptane mixtures are contained in small stoppered medicine dropper bottles. A drop of each mixture is placed on the fabric. The appearance of the test oil is observed through the drop. Note is made Whether wetting or penetration has occurred. The number corresponding to that mixture containing the highest percentage of heptane which does not penetrate nor 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 of zero oil/heptane rating, the symbol 0+ has been used to indicate a modicum of resistance to wetting by oil.

STAIN REPELLENCY Staining Tests in Anti-soiling Evaluation of the Resistance of Textile Fabrics to Waterand Oil-borne Stains The following procedures were established in the application of liquid staining materials more nearly approaching the materials producing waterand oil-borne stains to which household furnishings receive in actual daily use.

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

(b) Three inch medicine droppers are used to draw the stains from their containers. A one cubic centimeter calibration is established and is marked on the exterior of each dropper. The stains are squeezed vertically downward from a height 2 inches above the cloth.

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

Rating: Appearance No visible stain. 4 Slight stain. 3 Easily noticeable stain. 2 Considerable stain. l Very heavily stained.

(The spread or lack of spread is not necessarily reflected in these ratings.)

(d) Duplicate sets of stains are applied in separate areas so that one-half of the fabric can be washed. In most instances, the washing is carried out with 50 grams of FAB, in a cotton cycle, and a dummy load to total 5 pounds in a Norge Home Automatic Washer.

The following two lists describe the numbering system and organization of the stains on the fabric:

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 6 Oil stains:

(6) Wesson Oil (7) Gulf Supreme Motor Oil 20/20 (8) Oleomargarine (9) La Rosa Tomato Sauce (10) Jergens Lotion Eight cubic centimeters of dry powder per 200 cubic centimeters of Water applied at 160 F.

2 Melted and applied at 160 F.

(Those skilled in the art will recognize that, while these stains are not scientifically compounded, they are stains to which household furnishings are exposed in the use attendant upon everyday life.)

(When reporting the relative resistance to staining and relative ease of removing stain in laundering, the values from water-borne stains and oil-borne stains are averaged and reported. In all cases the stains are allowed to dry on the fabrics for twenty-four hours before washing.)

Household furnishings is a term used herein to designate all articles in the home of prince or pauper which are washed regularly at relatively frequent intervals or semi-occasionally at relatively irregular infrequent intervals. Household furnishings include bed linen, i.e., sheets, pillowcases, blankets, tablecloths, napkins, curtains, draperies, underthings, shirts, dresses, sox, handkerchiefs, blouses, skirts, slipcovers, and the like. It will be recognized that the term household furnishings is inclusive but not exclusive.

As everyone will recognize while the aforedescribed controlled staining tests are extremely useful for evaluating the effectiveness of various textile finishes, the incidence of staining a shirt front with salad oil (Wesson Oil) is only occasional whereas the staining of the collar and cuffs of a mans shirt with the finely divided soil of the environment mixed with the oily exudations of the healthy human skin is a moment-to-moment occurrence. Hence, important as the aforedescribed tests are, a test to evaluate the resistance of a finish to the pick-up of such soil, hereinafter designated oily particulate soil, i.e., a test to evaluate the ability to shed oily particulate soil and the ease with which such oily particulate soil is removed by laundering under controlled conditions of soiling is of greater importance. Such a controlled test providing reproducible results has been developed and is designated the GRC Dry Soil Test.

GRC DRY SOIL TEST Fifteen to twenty 6" x 8" numbered specimens (usually x 80 cotton), including at least one untreated control, are tumbled for thirty minutes with 10 percent Cyanamid Soil based on the weight of the fabric. The tumbling is carried out in a 5-liter capacity Five Minute Home Cleaner at 44 r.p.m.; six No. 8 Neoprene rubber stoppers are distributed among the speciments to increase the mechanical action. At the end of the tumbling, the specimens are removed and each shaken up and down separately fifteen times by hand to remove surface dirt.

The specimens are then cut in two, to produce two 4" x 6" pieces. One-half is washed with 50 grams of FAB in a cotton cycle with a S-pound dummy load, then hung to dry, and lightly ironed under a clean cotton cloth.

The degree of soil is determined with the Photovolt Reflectance Meter (Tri Blue Filter). Six readings per specimen are taken. The average of the six readings is reported.

CYANAMID SOIL The American Cyanamid Synthetic Soil described below is also recommended by the Minnesota Mining and Manufacturing Company. The dry ingredients are blended thoroughly, dried in a forced draft convection oven for eight hours at 50 C., then milled twenty-five hours with ceramic balls and stored in a polyethylene bag.

7 Material: Percent by weight Peat Moss 38 Cement 17 Kaolin Clay l7 Silica200 mesh 17 Furance Black 1.75 Red Iron Oxide 0.50 Mineral Oil 8.75

1 R. T. Vanderbilt Peerless.

2 Davidson Chemical Company.

Benny & Smith C0. Molacco.

* C. K. Williams C0.

It has been found that hydroxymethylated, fluoroacylated derivatives of aminohydroxy aromatic compounds having at least two active nuclear hydrogens may be used to treat textiles, i.e., fibers, yarns, fabrics, and the like composed of cellulosic, including natural such as cotton and regenerated proteinaceous including natural such as wool and synthetic fiber and particularly fibers having active hydrogen in the surface. It is to be observed that the compounds of the present invention can also be used for coating materials which do not have active hydrogen in the surface such as the polyalkylenes, e.g., polypropylene, and metals such as steel.

In general, the compounds of the present invention are prepared by methods of classical chemistry. Thus, an aromatic compound having one benzene ring or two or more fused rings is reacted in known manner to obtain the hydroxy compound. The latter is then reacted in known manner to obtain the amino hydroxy compound. While the single ring compounds are limited to a single amino and a single hydroxy group, i.e., paraaminophenol having two active nuclear hydrogens, the aromatic compounds having two or more fused rings can have one or a plurality of hydroxy groups and one or a plurality of amino groups provided the resulting compound has two active nuclear hydrogens. Thus, for example, the dimethylol derivative of paraaminophenol is illustrative of the single ring compounds while aminoalphanaphthol or 4-aminonaphthol is illustrative of the multi-ring compounds which can be used as starting materials for the preparation of the mono-methylol or dimethylol compounds of the present invention.

Illustrative of the preparation of a perfiuoroacyl derivative of paraaminophenol having the generic formula:

where Q is an alkyl group having 3 to 21 carbon atoms in which at least 70 percent of the 5 to 43 hydrogen atoms has been replaced with fluorine atoms and the terminal, i.e., omega carbon atom has at least two and preferably three fluorine atoms.

Thus, 0.1 mol of the butyl ester of perfluorooctanoic acid C F3(C F2)C| O CHzCI-IzCzlk is mixed with 0.1 mol of p-aminophenol, NH C H OH, and 225 parts by weight of methyl ethyl ketone. The reaction mixture was heated to reflux temperature (80 C.) for 3.5 hours to effect ammonolysis. The reaction can be The reaction mixture was stripped at elevated temperature to remove all solvents, i.e., methylethylketone and butyl alcohol. To 25 parts by weight of the stripped residue were added 5.5 parts by weight of percent methanol solution of formaldehyde. The pH of the mixture was adjusted to 11.4 by the addition of caustic soda and the reaction mixture heated two hours at reflux to effect methylolation. The methylolation of the perfluorooctoyl-paminophenol can be represented by the equation:

While the reaction represented by Equation 3 involves the reaction of the perfluoroacyl-p-aminophenol with formaldehyde in the molal ratio of l to 2, those skilled in the art will understand that the perfluoroacyl-p-aminophenol can be reacted with formaldehyde in the molal ratio of l to 1. Accordingly, the methylol derivatives of perfluoroacylaminohydroxy aromatic compounds having two active hydrogens have the generic formula:

o R. (Qd), HN .R( 0H (CH OID where R is the nucleus of an aminohydroxy aromatic compound having a single ring, two fused rings, or three fused rings, Q has the same significance as in Formula 1, R is hydrogen or alkyl having one to five carbon atoms, n is 1 or 2, m is one or two, t is one or two, s an integer 6, 8, or 10 minus (m+n+t), and x is the same as t.

The novel perfiuoroacyl aminohydroxy monomethylol and dimethylol compounds are not to be confused with prior disclosed compounds as simple methylol phenols. For example, in U.S. Pat. No. 2,468,530, the after treatment of viscose rayon to reduce the swelling value and increasing the water resistance and wet strength of viscose rayon with monoand di-substituted derivatives of monoand di-substituted phenols such as paracresol monoand di-alcohols represented by the formula:

where R is H or CH OH. However, these resins do not confer surface water or oil repellency to textile fibers.

The perfluoroacyl derivatives of aminohydroxy aromatic compounds are not to be confused with the perfluorinated cyclohexyl carboxylic acid and cyclohexyl acetic acid derivatives described in U.S. Pat. No. 2,593,737 having the composition represented by the generic formula RZ where R is a saturated polycarbon fluorocarbon radical containing at least three carbon atoms and Z is a monocarboxyl radical or a carboncontaining derivative radical hydrolyzable thereto such as C F COOH, undecafluorocyclohexyl carboxylic acid.

In U.S. Pat. No. 2,495,239 a method for treating cellulose is described. The patented method comprises condensing in alkaline medium para-tertiary-amyl phenol and formaldehyde in the molecular ratio of 1:2 and reacting the condensation product with cellulosic material containing free hydroxyl groups and subjecting the cellulosic reaction products to thermal treatment to form resiniform bridge linkages between the cellulose chains.

A process of rendering textile fabrics, yarns, and fibers waterproof without materially altering the general appearance of the fabric is described in U.S. Pat. No. 2,257,088. These results are produced by the use of compounds having the general structure in which Ar represents an aromatic nucleus of the benzene or naphthalene series carrying a nuclearly bound oxygen and at least one hydrocarbon substituent of the aliphatic or cycloaliphatic series which contains eight or more carbon atoms and which is bound to the aromatic nucleus directly or through an ether, carbonyl, carboxyl, or carbamido linkage. The nuclearly bound oxygen may be part of hydroxyl group or a part of a side chain. A and 13 represent members of the group consisting of open chain, lower aliphatic groups when taken singly and when taken together divalent groups which jointly with the nitrogen form a heterocycle.

'In direct contrast to the materials described in the foregoing U.S. patents, the compounds of the present invention are high melting point waxes which either react with active hydrogen in the substrate in the presence of an acid catalyst such as oxalic, phosphoric, and zinc nitrate, or form a coating on the substrate be it fibrous such as cotton, wool, nylon, polyethylene, wood, steel, aluminum, glass, or other ceramic having no active hydrogen when an alkaline catalyst such as NaOH, borax, and potassium methoxide is used.

Thus, for example, the dimethylol perfluorooctanoylaminophenol, the preparation of which has been described hercinbefore, can be suspended in water containing an acid catalyst, a fibrous material immersed in the water, the treated fibrous material squeezed to at least 80 percent Wet pick-up and the treated fibrous material heattreated at a temperature in the range of 250 to 300 F. for a period of time inversely proportional to the temperature and for example five to ten minutes at 300 F. (80 percent wet pick-up is a term meaning that the fibrous material contains 80 percent by weight based on the weight of the fibrous material of the aqueous suspension). Hence, when the suspension contains 1 percent by weight of the methylol derivative, the fibrous material contains 0.8 percent of the methylol derivative. Similarly, the methylol derivative can be dissolved in a suitable solvent, for example, xylene containing an acid catalyst, the fibrous material immersed in the solution of the methylol derivative, the fibrous material squeezed to the predetermined wet pick-up in the fibrous material, the solvent removed and the treated fibrous material heat treated as previously described.

On the other hand, any solid substrate with or without active hydrogen can be treated to provide the solid substrate with a coating of the polymerized methylol derivative. Thus, an aqueous suspension or a solution in a suitable organic solvent such as xylene containing an alkaline catalyst for example NaOCH ZnO, and triethanolamine can be applied to the solid substrate in any suitable manner as by dipping, spraying, spreading, or other means, the excess, if any, removed, and the treated solid substrate heat treated at elevated temperatures of at least 250 F. but below the decomposition temperature of the substrate or the methylol polymer for a period of time inversely proportional to the temperature, for example, at 300 F. for five to ten minutes.

Indicative of the waterand the oil-repellency and the resistance to soiling by oily particulate soil is the treatment of cotton with the bis-formaldehyde adduct to perfluorooctanoyl-p-aminophenol:

as HOHzG-(f (IJOH2OH ONHQ where M Q 18 a( 2)o Reflectance Oil repellency Before After Treatment applied obtained wash wash 3% product plus 0.5% Zn(NO3)2-6H2O 100 33 62 Accordingly, the present invention provides (1) novel monoand di-methylolamino hydroxy aromatic compounds, (2) fibrous or solid substrates having associated therewith polymerized monoand di-methylol aminohydroxy aromatic compounds, and (3) perfluoroacyl aminohydroxy aromatic compounds.

I claim:

1. A perfluoroacylaminohydroxy aromatic compound having a composition corresponding to the formula:

where R is an aromatic residue having at least two active hydrogens, selected from the group consisting of benzene and naphthalene nucleii; R is hydrogen or alkyl having one to five carbon atoms; Q is an alkyl group having three to twenty-one carbon atoms in which at least percent of the 5 to 81 hydrogen atoms has been replaced with fluorine atoms; n is 1 or 2; t is 1 to 2; x is the same as t; m is 0, 1 or 2; sis an integer 6 or 8 minus m-l-n-l-t.

2. A compound as defined in claim 1 wherein m is 0.

3. A compound as defined in claim 1 wherein m is 1 or 2.

4. A compound as defined in claim 2 wherein Q is pentadecafluorooctyl.

5. A compound as defined in claim 3 wherein Q is pentadecafiuorooctyl.

6. A compound as defined in claim 4 wherein n, t, and x are 1; R is hydrogen and s=4.

7. A compound as defined in claim 5 wherein m, n, t and x are 1; R is hydrogen and s=3.

8. A compound as defined in claim 5 wherein m=2; n, t and x are 1; R is hydrogen and s=2.

References Cited UNITED STATES PATENTS 2,4685 30 4/ 1949 Weeldenburg 8-1 16.4 2,495,239 1/1950 Drisch et al 8ll5.6 2,567,011 9/1951 Diesslin et al 260465.7 2,654,722 10/1953 Young et al. 260404 2,730,500 1/ 1956 Young et a1. 260404 2,799,692 7/1957 Croxall et a1. 260404 3,198,754 8/1965 Ahlbrecht et a1. 8--116.2 3,253,006 5/ 1966 Davis 260404 3,322,490 5/1967 Gagliardi 8-116.2 3,352,625 11/1967 Gagliardi 8-1l6.2 3,232,697 2/1966 Needleman 260404 3,244,734 4/ 1966 Sonntag 260404 LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner U.S. Cl. X.R.