US3427332A - Perfluoroalkyl amide derivatives of polyoxyalkylene carbamates - Google Patents

Description

United States Patent Office 3,427,332 Patented Feb. 11, 1969 3,427,332 PERFLUOROALKYL AMIDE DERIVATIVES F POLYOXYALKYLENE CARBAMATES Thomas Clark Allen, King of Prussia, and Robert Charles Koestler, Wayne, Pa., assignors to Pennsalt Chemicals Corporation, Philadelphia, Pa., a corporation of Pennsylvania No Drawing. Filed Sept. 5, 1967, Ser. N 0. 665,245 US. Cl. 260-404.5 14 Claims Int. Cl. C07c 125/04; D06m ABSTRACT OF THE DISCLOSURE This invention concerns novel carbamates containing terminal perfiuoroalkyl groups and their methylol derivatives which are particularly useful as textile finishes and other similar applications for imparting valuable stain repellancy and stain release properties.

This invention relates to novel fiuorinated compounds of particular utility for the treatment of textiles and other fibrous substrates to impart highly desirable stain repellancy and stain release properties.

The useful properties of compounds containing perfluoroalkyl groups for imparting both oleophobic and hydrophobic properties to textiles and other substrates are well known. A number of commercial textile finishes incorporating such compounds or polymers derived from them are now on the market. Commercial finishes of this type most commonly used fall into two main groups, viz. (1) Werner chromium complexes of carboxylic acids and (2) acrylate polymers. Both groups are characterized by the presence of relatively long perfluoroalkyl tails which are believed responsible for the unusual oil and water repellancy characteristics imparted by these ma terials.

While both classes of these materials have met with some success, they have been found subject to certain limitations and disadvantages. The chromium complextype materials have relatively poor hydrolyticstability and accordingly have relatively poor resistance to laundering. For this reason, their use has been confined mainly to the treatment of leather, paper, upholstery finishes and the like where resistance to laundering is not a requirement.

In the case of textiles made from natural or syntheic fibers or blends thereof which are frequently laundered or dry cleaned, fiuorinated acrylate polymers have been most frequently used, These are normally applied as a latex. Although these polymers give good resistance to oil and water-borne soils and are reasonably resistant to laundering, they have several important drawbacks. The most serious disadvantage is their poor stain release properties. By stain release is meant the readiness with which soils are removed from the textile on laundering or drycleaning. In general, soiling of textiles can occur in two ways. The first is by a wicking action of the fabric in which oily or aqueous materials are carried into the fabric by capillary action. The second soiling mechanism is that in which materials are rubbed into the fabric under pressure or deposited during laundering after being removed from the same or another fabric. Treatment of the fabric with fiuorinated acrylate polymers is quite effective in reducing soiling by the former mechanism since the fabric is rendered repellant both to oil and water soil carriers. Because of the repellancy properties imparted to the fabric, the oil or water-borne soil dies not penetrate and therefore soiling does not occur. However, the repellancy imparted by the acrylate polymers does not prevent soils from being rubbed into the fabric. Once this occurs, they become quite difficult to remove. In fact, experience has shown that soil that has been ground into fabrics that have been treated with fiuorinated acrylate polymers are considerably more difficult to remove than from untreated fabrics. For this reason, fabrics so treated are regarded as having poor stain release properties on laundering or drycleaning. A similar phenomenon, i.e., a deterioration of stain releasing properties, has been observed in the case of fabrics treated with so-called durable press or permanent crease chemicals which are designed to impart permanent wrinkle resistant and/or crease retention properties to the fabric such that it needs little or no ironing after laundering. Fabrics so treated have a pronounced tendency to retain rather than release ground-in soils on laundering. Treatment of durable press fabrics with fiuorinated acrylate polymers, while imparting improved stain repellancy does not significantly improve the stain release properties of the fabrics; the problem of removal of ground-in soils on laundering or drycleaning still remains.

The second disadvantage of the fiuorinated acrylate polymers is their poor compatability and stability with normal textile mill finishing baths. The fiuorinated acrylate polymers are applied to the fabric as aqueous latexes containing a variety of ingredients such as surfactants, initiators, cornonomers, modifiers, electrolytes and the like which must be present in an emulsion polymerization recipe. Because of the complexity of this mixture, it is often difiicult to produce stable combinations of these ingredients with the other ingredients of normal textile finishing baths which often include, among other things, emulsions, other polymer latexes, durable press chem icals, metal salts and the like, Furthermore, the latex, being an emulsion, can be coagulatcd by certain textile bath additives particularly if the ionic species are not the same.

A third disadvantage of the fiuorinated acrylate polymers is the tendency of the latex to coagulate and deposit a gummy mass in the bath, on the squeeze rolls, and even on the surface of the fabric due to the shearing forces caused by the mechanical action of the fabric passing through the bath and the rolls. Moreover, the latex polymer particles are easily coagulated in storage by any of a number of conditions such as exposure to light, low or high temperatures, a drastic change in pH or contamination with a variety of chemicals. These complexities and additional variables introduced by the use of the latex sometimes severely restricts the choice of textile bath additives that can be used.

According to the present invention, a group of new fiuorinated compounds has been discovered which overcome the disadvantages of prior fluorochemical textile treatments. These new compounds, when applied to textiles or other fibrous substrates, provide the desired high degree of repellancy to both oiland water-borne stains while at the same time, the stain release properties of the texitles on laundering or dry cleaning are greatly improved. In some cases, the textiles treated with compounds of the invention are superior in their stain release properties to the untreated fabrics. In the case of fabrics that have been subjected to a durable press treatment, the compounds of the invention, when applied to the fabric, overcome the poor stain release characteristics resulting from the durable press treatment, producing a fabric having durable press properties, good oil and water repellancy properties, and in addition, excellent stain release properties superior in many cases even tothose possessed by the untreated fabric. The compounds of this invention can also be used in conjunction with the fiuorinated acrylate polymers to impart stain release properties to fabric so treated.

An important advantage of the new compounds embodied herein is their compatability with the aqueous media normally used in textile treating operations. Many of the compounds are water-soluble viscous liquids, while the others are either solids or viscous liquids which are readily soluble in water-miscible organic liquids such as methanol or acetone, which solution is easily dispersed in Water to form very fine colloidal-like suspensions. The stain release agents compatibility with water makes it possible to apply the compound to the substrate treated therewith in a uniform amount throughout, and eliminates other difiiculties such as coagulation caused by ionic species, mechanical shear, chemical contamination and changes in temperature or pH.

The new compounds of the invention are fluorine-containing carbamates and their methylolated derivatives in which the fiuorinated portion of the molecule is a perfiuoroalkyl group. The fluorinated carbamates and their methylol derivatives may be represented by the generic formula:

where R is a perfluoroalkyl radical (straight chain or branched chain) having from 4 to 15 carbon atoms, preferably 6 to 12 carbon atoms; R is hydrogen or a lower alkyl radical (i.e. an open chain or cycloalkyl radical having about 1 to 6 carbon atoms) or a group; x is an integer from 1 to 1 00 inclusive and referably from 1 to 20 inclusive; R is a lower alkylene radical, straight or branched chain, having from two to about six carbon atoms and Y and Z (which may be the same or different) may be hydrogen, or the CH O-R group where R is hydrogen or a lower alkyl radical (i.e. an open chain or cycloalkyl radical having from about 1 to 6 carbon atoms). Where the group -(RO) is a repeating unit (i.e. where x is greater than one) the alkylene radical R can be the same or different in the repeating units in the chain as in the groups:

R (CHzCHzCHzO-CHzCHOCHZCH2O) where the alkylene radical R varies in the repeating units; or in the groups: (CH CH O) or (EH: (CHZCHO)! where the alkylene radical R is the same in the repeating units.

The fluorinated carbamates of the invention (which may be converted to the methylolated derivatives) may be represented by the general formula:

where R;, R and x are as defined above and where A is hydrogen, lower alkyl or a group.

A particularly preferred group of compounds within the general class defined above are the mono or dimethylolated carbamates of the general formula:

The above carbamates may be converted to mono or dimethylolated derivatives by techniques which are in themselves well-known, such as reaction with formaldehyde. By proper choice of conditions the monomethylol derivative can be made to predominate, or on the other hand a mixture of the mono and dimethylol derivatives or a product consisting mostly of the dimethylol derivative can be produced. If desired the alkoxymethyl derivatives can be obtained by concurrent or subsequent etherification of the methylol group with lower alkanols such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl alcohol or similar lower alkanols. Exemplary methylol derivatives of the carbamates of the invention 6 derived Lfrom the first compound listed above, are the following:

9 CHECK (CFMCF(CF2)7CC2H4OC-N\ O (I) CHzOH CHzOH It is understood of course that the similar derivatives may be prepared by methylolation of other carbamates within the scope of the invention.

A preferred procedure for preparing the new compounds of the invention involves as the first step the reaction of a perfluoroalkyl acid fluoride if RICF where R; is as above defined with a primary or secondary amino alcohol to form an amido alcohol. An alternate route to the amido alcohol is the preparation of the amide 0 Ri -NEE where R: and R are as defined above followed by reaction of the amide with an alkylene oxide such as ethylene oxide. If additional oxyalkylene groups (RO) are desired, the amido alcohol may be reacted with an alkylene oxide such as ethylene oxide or propylene oxide forming a longer chain amido alcohol with repeating oxyalkylene groups, e.g. ethylene oxide groups: (CH CH O) The resulting amido alcohol is then converted in a second step to the ca-rbamate by any one of several alternative procedures.

The carbamate may then be converted in a third step to a methyl derivative preferably by reaction with formaldehyde. If alkoxymethylol derivatives are desired the methylolation is carried out in the presence of an alkanol or alternatively the methylolated product may be reacted with an alkanol in a separate step.

In the first step of the above procedure, namely the preparation of the amido alcohol,

tert butyl may be used. The reaction of the amino alcohol with the perfluoroalkyl acid fluoride H RICE may be conveniently carried out at temperatures of from about 10 C. to about 60 C. and preferably from 10 C. to 20 C. in a solvent such as chloroform or methylene chloride employing mole ratios of amino alcohol to perfluoroalkyl fluoride of from about 2:1 to 4:1 and preferably 2:1 to 2.5 :1. After formation of the amido alcohol, the alcoholic hydroxyl group thereof may be reacted with an alkylene oxide such as ethylene oxide or propylene oxide if it is desired to add one or more repeating oxyalkylene groups to the molecule. The addition of the alkylene oxide may be conveniently carried out at temperatures of about 20 C. to 150 C. and preferably 100 C. to 130 C. Generally the addition is carried out in a sealed vessel in the absence of a solvent using a basic catalyst such as sodium hydroxide, sodium methoxide or the like.

The second step of the preparative procedure described above, i.e., the carbamylation of the amido alcohol Rri. 1N(RO) ,H to obtain the carbamates of the invention,

may be carried out in a number of ways. One suitable method is the reaction of the amido alcohol with sodium cyanate and trifluoroacetic acid in an aromatic solvent following the carbamylation technique of Loev and Kormendy, J. Org. Chem. 28 p. 3421 (1963).

A second carbamylation technique is the reaction of the amido alcohol with an excess of urea in the presence of a small amount of a catalyst such as zirconium acetylacetonate or zinc acetate dihydrate, generally at temperatures of from about 120 C. to 220 C.

A third and often preferred carbamylation method is the reaction of the amido alcohol with an alkyl carbamate such as ethyl carbamate,

ll CHaCHzOCNHz in a hydrocarbon solvent at temperatures generally ranging from about 80 C. to 150 C. The ethanol formed as a byproduct is preferably continuously removed from the reaction mixture e.g. by distillation.

The third step in the preparative procedure described above, namely, the methylolation of the carbamates of the invention,

0 A R.l'; (R'o tNH. is conveniently carried out by reaction of the carbamate with formaldehyde preferably in basic methanol solution or basic aqueous solutionpThe completeness of methylolation depends on the reaction conditions. Excess formaldehyde, higher temperatures, longer reaction times and high pH values in general favor more complete methylolation.

Generally, the methylolation is carried out at temperatures of from 30 C. to 100 C. and preferably from 60 C. to 80 0., mole ratios of formaldehyde to carbamate of from 1:1 to 10:1 and preferably 1:1 to 5:1, and at a pH ranging from 6 to 12 and preferably from to 11, and for reaction periods ranging from 10 minutes to 24 hours and preferably from 2 to 3 hours. Depending on the reaction conditions chosen, one or both of the hydrogens of the carbamate group i --ONH2 may be replaced by methylol groups CH OH. If the alkoxy methyl derivatives of the carbamates are desired, the methylolation is ran in the desired alkanol solvent at an alkaline pH followed by etherification by adjusting the pH to a relatively low acid pH, e.g. pH of 1 or 2.

PREPARATION OF CARBAMATES The following examples illustrate the preparation of the new carbamates of the invention:

Example 1A.-Preparation of I II 0 F920 F (CFzhil-Ifi-CEDCHEO CHzCHzOC-NHs parts by weight of is added to a solution of 40 par-ts (all parts are by weight) of diglycolamine alcohol (NH C H OC;H OH) in 330 parts of chloroform under a nitrogen blanket at a temperature of 20 to 25 C. The reaction is carried out with agitation at this temperature for one hour to give a clear solution which is then washed with an aqueous solution containing 5% NaCl and 5% HCl, followed by two more washings with 5% aqueous NaCl solution. The organic layer is separated and the chloroform is stripped from the organic layer to yield the solid amido alcohol product M.P. 45-46.5 C.

AnalysiS.Calculated for C H F NO C, H, 1.55%; N, 2.15%. Found: C, 27.38%; H, 1.67%; N, 2.07%.

The foregoing alcohol is converted to the carbamate as follows:

parts of the above amido alcohol is mixed with 26 parts of NaOCN in 880 parts of benzene at 50 C. Trifluoroacetic acid (45.6 parts) is added dropwise and the mixture is stirred for two hours at 6570 C. Water (500 parts) is added, the mixture heated to boiling, and more benzene (800 parts) is added to ensure dissolution of all organic materials. The benzene and aqueous layers are separated while hot and the benzene layer is dried by stripping olf the water azeotrope. The benzene solution is cooled and the carbamate product having the structure (CFa)2CF(CF2)1( -I IC2H 0CzHtOil-NH: (90 parts, yield 64%) crystallizes and is recovered; M.P. 100 to 101 C. The structure of this compound is confirmed by infrared spectroscopy and elemental analysis.

Example 1B.Preparation of 32.5 parts (0.05 mole) of the amido alcohol prepared according to Example 1A, six parts (0.06 mole) of urea and 0.5 part zinc acetate dihydrate are mixed and stirred for five hours at ISO- C. The reaction mixture is taken up in acetone and the solution filtered. Evaporation of the acetone and recrystallization of the crude product from benzene yields the carbamate,

in about 72% yield, M.P. 100-101 C.

Example 1C.Preparation of 65.1 parts (0.1 mole) of the amido alcohol prepared in Example 1A, 10.7 parts (0.12 mole) of ethyl carbamate, and 50 parts of toluene are brought to reflux and about 4 parts of distillate are taken off to ensure an anhydrous system. 0.3 part of tetraisopropyl orthotitanate is added and the mixture is refluxed for about 4 hours during which time the ethanol lay-product is taken off as an ethanol-toluene azeotrope. 50 to 75% of the toluene is distilled off and the residue is poured into a dish where it solidifies and is air dried to yield the carbamate,

(C a)2C 2)1 -I I-(C2H4O)zi NHz (69.4 parts, 100% yield) M.P. 100 to 101 C.

Example 2.-Preparation of The acid fluoride (33.9 g., 0.058 mole) is dissolved in 300 milliliters of anhydrous ether and cooled in an ice bath. Diglycol amine alcohol (H NC H OC H OH) (12 g., 0.116 mole) is added slowly while stirring under a nitrogen blanket. The mixture is then refluxed for 13 hours. A precipitate forms which is filtered 011 and the ether is evaporated from the filtrate to give 36.2 grams (95% yield) of a white waxy solid having a melting point of 74-77 C., the infrared spectrum of which shows no ester peak, which is the amido alcohol The amido alcohol prepared as described above (35.4 grams, 0.0471 mole) and 6.1 grams (0.0942 mole) of sodium cyanate are stirred at reflux in 150 milliliters of benzene. Trifluoroacetic acid (10.7 grams, 0.0942 mole) is added dropwise and the reaction refluxed for /2 hour. Water is added and the benzene and water layer is decanted from the product. The product is then taken up in a mixture of 100 milliliters of hot water and 50 milliliters of hot ace-tone. The layers are separated and the solvent evaporated from the organic layer. The carbamate is obtained as a white crystalline solid (32.3 grams, 86%

yield) which after recrystallization from toluene shows a melting point of 113-1 15 C.

Analysis.-Calculated for C H F N O C, 27.2% H, 1.39%; N, 3.52%. Found: C, 27.64%; H, 1.71%; N, 3.41%.

Example 3.--Preparation of O H i 920 F (C MC-g-CzHMO CzHrO--NHz The amido alcohol is prepared by the reaction of the acid fluoride crude product. Recrystallization of the crude product from toluene gives the carbamate 0 0 ll 1 0 F920 F c Fmo-ig-omomo omomo-d-mn having a melting point of 84-86" C.

Analysis.-Calculated for C H F N O C, 28.3%; H, 1.85%; N, 4.72%. Found: C, 28.29%; H, 2.01%; N, 4.57%.

Example 4.Preparation of The acid fluoride (36.6 grams, 0.1 mole) is added dropwise to diglycol amine alcohol, H NCH CH OCH CH OH, (23.1 grams, 0.22 mole) while stirring and cooling with an ice bath. After standing 1 hour and warming to room temperature, 50 milliliters of 15% HCl and 50 milliliters of trichlorotrifluoroethane are added to the reaction mixture. The layers which form are separated. The organic layer is washed with 10% sodium bicarbonate. The layers are then separated and the organic layer is dried over anhydrous sodium sulfate. Removal of the trichlorofluoroethane solvent by heating to 140 C. gives 34.7 grams (77% yield) of a clear colorless liquid, the infrared spectrum of which is free from ester bands, and which is the amido alcohol:

II (0 F920 F (o mac-g-omcmoomcmon Analysis.-Calculated for C H F NO z C, 29.3%; H, 2.22%; N, 3.11%. Found: C, 28.96%; H, 2.35%; N, 2.71%.

The amido alcohol, prepared as described above (34.7 grams, 0.077 mole) and sodium cyanate (10.0 grams, 0.154 mole) are stirred in milliliters of methylene chloride. Trifluoroacetic acid (17.6 grams, 0.154 mole) is added dropwise at room temperature. The mixture is stirred for 1 hour. The water is added and the layers separated. The organic layer is dried over anhydrous sodium sulfate and the solvent evaporated. There is obtained 22.8 grams 60% yield) of a white crystalline solid which after recrystallization from toluene has a melting point of 62- 64 C. and the structure 0 (oFmcF(GFzhii-O-CzHrOCzHr-OdNHz Analysis.Calculated for C H F N O C, 29.15%; H, 2.23%; N, 5.67%. Found: C, 29.31%; H, 2.47%; N, 5.67

Example 5 .--Preparation of A mixture of acid fluoride consisting of 70% by weight of the acid fluoride and 30% by weight of (CFa)2CF(CF2) CF is added dropwise to a mixture of a polyglycolamine alcohol of the formula H N(C H O),.H, where x has the value of 10-11, in an equal weight of methylene chloride at room temperature. The acid fluoride is added to the polyglycolamine alcohol in a molar ratio of 1 mole of acid fluoride to 2 moles of polyglycolamine alcohol. After stirring for 1 hour, water is added and the aqueous and organic layers separated. The organic layer is washed with and is obtained.

1.0 mole of the above mixture of amido alcohols, ethyl carbamate,

ll CzHaO-C-NHz (1.15 mole) and toluene (400 milliliters) are mixed and brought to reflux. 40 milliliters of toluene is distilled off to dry the system. Tetraisopropyl orthotitanate milliliters) is added. The mixture is refluxed and a tolueneethanol azeotrope boiling at about 76-80 C. is removed as it is formed. When azeotrope removal is complete, the toluene is distilled 01f and the product obtained is a mixture of the carbamates and Example 6.Preparation of:

Ethanol amine, H NCH CH OH, (427 grams, 7.0 moles) is suspended in 4.0 liters dry ethyl acetate, cooled by an ice bath. The acid fluoride,

having a melting point of 87.5-88.5 C.

The amido alcohol prepared as described above (60.7 grams, 0.1 mole) and sodium cyanate (13.0 grams, 0.2 mole) are stirred and warmed in a mixture of 85 milliliters of trichlorotrifluoroethane and 165 milliliters of benzene. Trifluoroacetic acid (22.8 grams, 0.2 mole) is added dropwise. A precipitate is formed and is filtered off. The precipitate is then taken up in 200 milliliters of acetone and poured into ice water. The product is filtered off and air dried. After recrystallization from a 3:1 tolueneacetone mixture there is obtained (52 grams, 80% yield) of the carbamate having a melting point of 109-111 C.

Analysis.Calculated for: C H F N O C, 25.50%; H, 1.19%; N, 3.76%. Found: C, 25.85%; H, 1.07%; N, 4.31%.

Example 7.Preparation of:

O CH: (C F3)2C F (O Fz)1 I ICH2CH20 -NHz The acid fluoride (70 grams, 0.1237 mole) is added dropwise to a stirred mixture of N-methylethanolamine,

HN (CH CH CH OH (18.6 grams, 0.248 mole) in 100 milliliters of methylene chloride under a nitrogen blanket. After about 1 hour of stirring at room temperature, 50 milliliters of water is added and the layers which form are separated. The organic layer is dried over anhydrous sodium sulfate and there is obtained 56 grams (76% yield) of semi-solid crystals, showing little or no ester bands in the infrared spectrum, and having the structure 0 CH3 (CF3)2CF(CF2)1 I ICHzCH2OH The amido alcohol prepared as described above (12.4 grams, 0.02 mole) and sodium cyanate (2.60 grams, 0.04 mole) are stirred at 25 C. in 50 milliliters of benzene. Trifluoroacetic acid (4.56 grams, 0.04 mole) is added rapidly to the mixture which is then heated at 80 C. for 10 minutes and then stirred for 1 hour at 25 C. Water and acetone are added and the mixture is heated to dissolve all lumps. The mixture is then cooled and the layers separated. The organic layer is washed with water and dried over sodium sulfate. The benzene is evaporated to give 7.6 grams of white solid (57% yield) which upon recrystallization from benzene has a melting point of 84- 85.5 C. and the structure ii I n (CF3)2CF(CFz)7CN-CH2CH2OC-NH2 Analysis.Calculated for C15H9F21N2O3: c, 27.1%; H, 1.35%; N, 4.22%. Found: C, 26.58%; H, 1.40%; N,

Example 8.Preparation of:

One mole of is added dropwise to a mixture of the polyglycolamine alcohol One mole of the amido alcohol prepared as described above is mixed with ethyl carbamate (1.1 mole) in 400 milliliters of toluene. The mixture is heated at reflux and about 40 milliliters of toluene are distilled off to remove water, after which there is added 10.0 milliliters of tetraisopropyl orthotitanate catalyst. The toluene-ethanol azeotrope is removed at about 76-80 C. after which the excess toluene is distilled oif to obtain the carbamate Example 9.-Preparation of:

One mole of the acid fluoride is added dropwise to a mixture of 2 moles of tertiary butyl amino ethanol (EH3 CHaC-NHCHzCHrOH in an equal weight of methylene chloride at room temperature with stirring. After one hour of stirring at room temperature, a small amount of water is added and the layers which form are separated. The bottom layer is washed once with diluted HCl and once with water. After drying over anhydrous sodium sulfate, the solvent is evaporated to give the amido alcohol Example 10.Preparation of:

One mole of the acid fluoride is added dropwise to a stirred mixture of 2 moles of propanolamine H NCH CH CH OH, in an equal weight of methylene chloride at room temperature. After one hour of stirring at room temperature, a small amount of water is added and the layers which form are separated. The organic layer is washed once with dilute-HCI and then with water, dried over anhydrous sodium sulfate and the solvent removed to give the amido alcohol One mole of the amido alcohol prepared as described above is treated in an autoclave at a temperature of 140 C. with ethylene oxide (3 moles) in the presence of a small amount of sodium hydroxide for about 20 hours. There is obtained the amido alcohol of the structure H oFmomnc-g-wmomomm (CH2CH20)x-:H

One mole of the ethylene oxide addition product prepared as described above is refluxed with about 1.1 moles of ethyl carbamate in 400 milliliters of toluene. A small amount of toluene is distilled oif to dry the system after which there is added 10.0 milliliters of tetraisopropyl orthotitanate. The toluene-ethanol azeotrope boiling at about 76-80 C. is removed after which excess toluene is distilled off to obtain the carbamate of the structure Example 1l.Preparation of:

Diethanolamine (42.0 grams, 0.4 mole) is mixed with 200 milliliters of methylene chloride. The acid fluoride (113.2 grams, 0.2 mole) is added dropwise to the stirred mixture at room temperature. After standing one hour the top layer is decanted and discarded. Ethyl acetate milliliters) is added and the mixture heated to reflux. The mixture is cooled and rfiltered to remove 23 grams of the amine salt HF-NH(C H OH) The filtrate is evaporated to yield 129.4 grams (99% yield) of a syrup which slowly crystallizes. This material, the infrared spectrum of which shows little or no ester band, has the structure:

The amido alcohol prepared as described above (20 grams, 0.0308 mole) is heated with urea (5.0 grams, 0.083 mole) at 150 to C. with stirring for 3 hours in the presence of 0.3 grams of zirconium acetylacetonate as a catalyst. A thick grease is obtained in 82% yield, the infiared spectrum of which confirms the carbamate:

0 CHzCHaO-(J-NH:

(CFDCF (C F2)1UN CH2CH20-(J-NH2 Example 12.Preparation of:

Following the procedures of Example 11, the acid fluoride is added dropwise to a stirred mixture of dipropanol amine, HN(CH". OH CH OH) in methylene chloride using a molar ratio of dipropanolamine to the acid fluoride of 2:1. The amido alcohol:

0 I 3)2C 2).5(LN(CH2CHzCH2OH)2 obtained from this reaction is then reacted with urea at about 150 C. in the presence of zirconium acetylacetonate as a catalyst using a molar ratio of urea to the amido alcohol of about 3:1. The carbamate is obtained having the structure:

CHzCHzCHzO JNH2 (CFa)zCF (OF2)aC-N CH2CH2CH2O -NH2 METHYLO'LATION OF CARBAMATES 1.0 mole of the carbamate having the above structure prepared in accordance with Example 1A is mixed with 1.0 mole of formaldehyde as a 37% aqueous solution. The mixture is made basic to a pH of 9 by the addition of NaOH. After heating with stirring at 50 C. for 2 hours during which the pH drops to about 6 the mixture is then cooled. The product obtained is mostly the monomethylol derivative:

H o /CH20H (CFO-20F(OF2)1C-N-(C2H4O)2CN H Example 14.Methylolation of using an excess of formaldehyde in methanol solution. 90 grams (0.13 mole) of the carbamate having the above structure and prepared in accordance with Example 1A and 42.2 grams of a 37% aqueous formaldehyde solution (containing 0.52 mole CH O) are dissolved in 400 milliliters of methanol. 20' drops of a 50% NaOH solution are added and the mixture is refluxed for about 12 hours. The solution is then neutralized with acetic acid and filtered. There is obtained a methanol solution of the methylol derivative of the above carbamate consisting mostly of the dimethylol carbamate of the structure:

0 CHZOH CHzOH CHzOH Example 16.Preparation of the ethoxymethyl derivative of 34.7 grams (0.05 mole) of the carbamate of the above structure prepared in accordance with Example 1A is dissolved in 35 grams of absolute ethanol. 3.75 grams (0.125 mole) of paraformaldehyde is added to this mixture after which the pH is adjusted to with 50% NaOH. The mixture is heated for 45 minutes at 50 C. and then the pH is adjusted to 1.0 with concentrated HCl. After stand- 16 ing over night, the pH is adjusted to 6 by the addition of NaOH. The resultant product, which is very soluble in hexane, consists mostly of the diethoxymethyl derivative having the structure:

u (I) CH20C2H5 (CFa)2CF(CF2)7C-}li(CzH40)zC-N CH2OCzH5 Example 17.-Preparation of the cyclohexyl ether of the dimethylol derivative of 34.7 grams (0.05 mole) of the carbamate of the above structure prepared in accordance with Example 1A is mixed with 10.0 grams of formaldehyde as a 37% aqueous solution (containing 0.125 mole CH O). The mixture is made basic to a pH of 10 by the addition of 50% NaOH after which the mixture is stirred and heated at 50 C. for 45 minutes. Cyclohexanol (34.7 grams, 0.1 mole) is added together with enough HCl to bring the pH to 1. The mixture is allowed to stand at room temperature for about 12 hours and then is neutralized with NaOH. The material is dried with anhydrous sodium sulfate and then filtered to give a thick colorless liquid consisting mostly of the cyclohexyl ether of the dimethylol derivative of the carbamate, having the structure:

Example 18.Methylolation of:

24.3 grams (0.344 mole) of the carbamate having the above structure prepared in accordance with Example 2 is dissolved in 107 grams of methanol. 11.1 grams of a 37% aqueous solution of formaldehyde (containing 0.137 moles of CH O) is added plus a few drops of 50% NaOH. The mixture is brought to reflux and 50% NaOH is added fiom time to time to keep the pH at about 9.5. The reaction is stopped after 18 hours of reflux. The product which is obtained as a 20% solution in methanol consists mostly of the dimethylol derivative having the structure 20.0 grams (0.0337 mole) of the carbamate of the above structure prepared in accordance with Example 3, is mixed with 11.0 grams of a 37% aqueous formaldehyde solution (containing 0.135mole CH O). A few drops of NaOH solution is added and the mixture is stirred and warmed to 60 C. for 18 hours. A soft, watersoluble grease is obtained containing 65% solids which consists mostly of the dimethylol derivative having the structure:

omoH Example 20.Methylolation of:

22.0 grams (0.0445 mole) of the carbamate having the above structure prepared in accordance with Example 4 is mixed with 86.6 grams of methanol and 14.4 grams of a 37% aqueous formaldehyde solution (containing 0.178 mole CH O). The mixture is made basic by the addition of a few drops of 50% aqueous NaOH and refluxed for 18 hours. The product, which is obtained as a 20% solution in methanol consists mostly of the dimethylol derivative having the structure:

1.0 mole of the mixture of carbamates prepared in accordance with Example is mixed with 4 moles of formaldehyde as a 37% aqueous solution. The mixture is brought to a pH of by the addition of aqueous NaOH after which the mixture is heated at 60 C. for 2 hours. The mixture is then neutralized to a pH of 6 by the addition of acetic acid. The product obtained, which is dissolved in methanol to give a 50% methanol solution, consists mostly of the dimethylol derivative of the structure:

CHzOH Example 22.Methylolation of:

30.6 grams (0.0472 mole) of the carbamate of the above structure prepared in accordance with Example 6 is mixed with 15.3 grams of a 37% aqueous formaldehyde solu tion (containing 0.189 mole CH O) and 121 grams of methanol. A few drops of 50% aqueous NaOH solution is added and the mixture refluxed for 18 hours. NaOH solution is added from time to time to keep the pH near 9.5. The product, which is obtained as a solution in methanol, consists mostly of the dimethylol derivatives of structure:

T) IO CHzOH (OF3)2CF(CF2)7-CH2CH20-N CH2OH Example 23.-Methylolation of:

ii i n (CFzOzCF(CF2)1CNOH2CHQOCNH2 13.3 grams (0.02 mole) of the carbamate having the above structure prepared in accordance with Example 7 is stirred at 50 to 60 C. with 6.5 grams of a 37% aqueous formaldehyde solution (containing 0.08 mole CH O) together with a few drops of 50% NaOH solution, and stirring is continued for about minutes. The pH is adjusted to about 6 by addition of acetic acid. The product, which is obtained as a 50% methanol solution by the addition of 9 grams of methanol, consists mostly of the dimethylol derivative of the structure:

$1) (3H3 /CH2OH (CFa)2CF(OF2)vCNCH2CHzOC-N CHzOH Example 24.-Methylolation of:

n it (CFB)2CF(CF2)7C-N(CH2CH2OC-NH2)2 18.0 grams (0.0244 mole) of the carbamate having the above structure prepared in accordance with Example 11 is mixed with 11.5 parts of a 37% aqueous formaldehyde solution (containing 0.142 mole CH O). A small amount of NaOH solution is added to bring the pH to about 9. The mixture is stirred at room temperature and becomes homogenous. The water soluble product consists mostly of dimethylol derivative of the structure:

(I) CHzOH CHzCHzO--N CHzOH (H) COHHz CHzOH APPLICATION TO FABRICS AND THE LIKE As previously pointed out, the compounds of the invention have the valuable property of imparting both stain repellancy and stain release characteristics to fabrics and other fibrous substrates. They are elfective on fabrics and other substrates composed of both natural and synthetic materials such for example as cellulosic materials, polyamides, acrylics, polyesters, glass fibers etc. The compounds of the invention are especially suitable for application to cellulosic fabrics, i.e., fabrics, whether woven or not woven, containing cellulosic fiber, such as cotton fabrics, mercerized cotton fabrics, rayon fabrics, linen, flax, cellulose acetate or the like, as well as blends of such cellulosic fibers with other materials such as wool, nylon, acrylic fibers, polyolefin fibers, glass fibers, polyester fibers and the like.

Desirable properties may also be imparted to other fibrous substrates such as leather, paper, hemp, wood or the like.

The compounds of the invention may be applied to the fabric or the substrate by contact with an aqueous or organic solution, or dispersion of the compound. Application to fabrics is preferably by the commonly employed technique of padding. Application from aqueous pad baths is generally preferred; however, other pad bath media containing organic solvents such as alcohols, ke tones, halogenated hydrocarbons, aromatic or aliphatic hydrocarbons may be used. The pad bath mixture will generally contain from about 0.05 to 10% and preferably from about 0.1% to 1% by weight of the compound of the invention, preferably together with a curing agent to promote the fixation of the compound on the fabric such as magnesium chloride, zinc chloride, zinc nitrate, aluminum chloride, ammonium chloride, zinc fluoro borate, magnesium fluoroborate, dimethylaminomethylamine hydrochloride, hydroxyacetic acid, magnesium hydrogen phosphate, citric acid, oxalic acid, 2-methyl-2- aminopropanol hydrochloride, magnesium nitrate, strontium nitrate, zinc acetate, or similar agents known in the art. To assist in fixing the compounds of the invention on the fabric a curing agent will generally be added to the pad bath in amounts ranging e.g. from 10% to 50% by weight based on the weight of the compound.

The amount of the compound deposited on the fabric as it travels through the pad bath can be controlled by well-known techniques such as the concentration of the compound in the pad bath media, the amount of excess of the .pad bath which is squeezed out of the fabric by passage through the squeeze rolls and the like. It will be generally advantageous to control the add-on to the fabric such that the treated fabric is impregnated with about 0.05 to 10 and preferably from about 0.1 to 1% by weight of the compound of the invention based on the weight of the dry fabric.

If desired, the pad bath containing the compound of the invention may also contain other pad bath additives for imparting particular properties to the fabric, such as durable press agents, optical brighteners, stiifeners, softeners, abrasion protectors, biocides, biostats and the like. As previously mentioned, a prime advantage of the compounds of the invention is that they are generally stable in the presence of these other bath additives, providing bath stability and ease of operation.

A particularly advantageous use of the compounds of the invention is the treatment of fabric, particularly cellulosic fabric, in combination with the so-called durable press chemicals which are used to impart wrinkle recovery and crease retention properties to the fabric. Preferably, the compounds of the invention are applied simultaneously from the same pad bath containing such durable press agents.

Such agents are well-known in the art and include, e.g. formaldehyde, the reaction products of formaldehyde with urea and substituted ureas such as 2-imidazolidinonc, 4,5-dihydroxy-2-imidazolidinone, tetrahydro-2 pyrimidinone, 5-(u-hydroxyethyl)tetrahydro-s-triazin-2-one, tetrahydro-l,3,5-oxadizin-4-one, and the like, the reaction products of formaldehyde with s-triazines such as melamine and the like, the reaction products of formaldehyde with hydrocarbon esters of carbamic acid such as methyl carbamate, hydroxyethyl carbamate, methoxyethyl carbamate and the like.

Following application of the compounds of the invention, e.g. from the pad bath, with or without simultaneous addition of other impregnating materials, the impregnated textile or other material is subjected to drying; and may also be subjected to a curing operation to fix the impregnants on the fabric. After drying at temperatures e.g. from 25 to 170 C. for about 1 to 60 minutes ,the impregnated material is subjected to curing temperatures of e.g. from 120 to 180 C. for about 1 to 25 minutes, with longer curing times being employed at the lower temperatures and conversely.

It has been found that the final properties of the treated fabric are dependent to some degree upon the paddnig and curing conditions employed, particularly the type of durable press agent, the type of curing catalyst and the curing temperatures. In particular it has been found that the water repellancy of the fabric may be varied from relatively low values where this is desirable (such as in shirt fabrics where low water repellancy for wearer comfort is desired) to relatively higher water repellancies where this is the desired characteristics.

The preferred compounds of the invention for producing a combinationof stain repellancy and stain release effects on textiles and other fiber substrates are the methylol derivatives of the carbamates of the invention, particularly the methylolated derivatives containing one or more methylol (CH OH) groups. Included in the term methylolated derivatives are also the alkoxy methyl derivatives, i.e. those containing a CH OR group where R is a lower alkyl group as previously defined. The methylolated derivatives containing the free methylol (i.e. the unetherified) methylol groups are preferred since these have higher water solubility and are thus more compatible with aqueous padding baths.

The methylolated derivatives of the carbamates are in general preferred over the carbamates themselves for stain repellancy and stain release applications in that, in general, they give somewhat higher stain repellancy and stain release ratings and also because the textiles so treated retain these properties over a longer series of laundering and/or dry cleaning. It is believed that the methylolated derivatives have fiber reactive properties, particularly with respect to cellulosic textiles by reaction of the methylol or alkoxy methylol gruops with the fiber substrate.

The carbamates themselves have useful stain repellancy and stain release properties when applied to textiles and the like and thus have a direct use for this purpose. Also the carbamates are, of course, the intermediates for the preparation of the methylolated derivatives.

It has been found in general that the greater the number of (RO) groups that are present in the compounds of the invention, the greater will be the water solubility of the compound (thus making it more compatible with aqueous pad baths). It also has been observed that in general the greater the number of (RO) groups, the

less pronounced are the water repellancy properties of the treated fabric. Reduced water repellancy may be desirable for some applications, e.g., for the treatment of shirt fabrics where a high degree of water repellancy is not desirable because of wearer-comfort considerations and the like.

The following examples illustrate the highly desirable combination of stain repellancy and stain release properties imparted to textiles by the compounds of the invention.

In order to provide a standard basis for comparison, a standard pad bath formulation containing a commercially widely used durable press additive was prepared. This standard pad bath, designated as pad bath A has the following compositions:

1 Rohm and Haas Rhoplex HA-8 (45% solids).

2 Sun Chemical Mykon SF (25% solids).

Using the above standard pad bath formulation, a series of tests was made, first using no additive (Example A in Table I) and using Pad Bath A plus 1% by weight of various compounds of the invention (Examples B to K in Table I). In each test, a Dacron 54 polyester/cotton (65% polyester/35% cotton), poplin fabric test piece is padded through the bath at a 6575% wet pick-up, is air dried at room temperature for at least 60 minutes and then heat cured at 170 C. for 3 to 5 minutes.

The pieces of test fabric are then evaluated for Hydrocarbon Repellancy Rating, Stain Repellancy Rating and Stain Release Rating. These evaluations are carried out as follows:

Hydrocarbon repellancy rating.In this test, the repellancy of the fabric pieces to oily liquids is tested using the A.A.T.C.C. Tentative Test Method 119-1966 T, Oil Repellancy, Hydrocarbon Resistance Test. According to this test, drops of standard test liquids consisting of a selected series of hydrocarbons with varying surface tension, are placed on the fabric surface. The Hydrocarbon Repellancy Rating is defined as the highest number test liquid which does not wet the fabric surface. The higher the Hydrocarbon Repellancy Rating therefore, the better the repellancy of the fabric to oily materials. Wetting of the fabric is normally indicated by a darkening of the fabric at the liquid-fabric interface. The following standard test liquids and rating system are employed:

Test liquid Hydrocarbon repellancy rating Fabric wetted by mineral oil 1 0 Fabric not wetted by mineral oil 1 1 Fabric not wetted by 65:35 mixture of mineral oil: n-hexadecane 2 Fabric not wetted by n-hexadecane 3 Fabric not wetted by n-tetradecane 4 Fabric not wetted by n-dodecane 5 Fabric not wetted by n-decane 6 Fabric not wetted by n-octane 7 Fabric not wetted by n-heptane 8 1 Saybolt viscosity 360/390 at F., sp. gr. 0880/0900 at 60 F. (e.g. Nujol).

Stain repellancy rating.In this test, a series of eight staining materials is employed including both oil base and water-based materials viz., (1) SAE 30 motor oil; (2) spaghetti sauce; (3) French dressing; (4) bacon grease; (5) Vaseline hair tonic; (6) Mazola corn oil; (7) mayonnaise; (8) mustard. The test fabric is placed on blotting paper and three drops of each stain are dropped onto the fabric from a height of about one foot. The stain is allowed to stand one minute and all that has not penetrated is then carefully scraped off with a spatula. The stain impact area is then rubbed lightly with a soft paper tissue, following which the stain re contrast, in Examples B through K inclusive, wherein 1% by weight of various compounds of the invention were incorporated in the standard durable press pad bath, good to excellent repellancy ratings were obtained both in the hydrocarbon repellancy and stain repellancy tests.

pellancy evaluation is made according to the following 5 In the stain release test moreover, very good to excellent rating scale using as the standard for comparison an unstain release ratings were obtained in each case demonstrattreated fabr1c specimen (not padded through Pad Bath ing the greatly increased launderability imparted by the A) which has been sub ected to the above stain in the compounds of the invention. Thus, the use of a small same manner. amount of the compounds of the invention not only Table I Hydrocarbon Stain Stain Pad Bath A Plus Repellancy Repellancy Rating Rating Rating (Static Soils) Example:

A.. No additive (control) 1 7 B 1% by wt. of Compound of Ex. 1 8 24 0.. 1% by wt. of Compound of Ex. 6 32 38 D 1% by wt. of Compound of Ex. 28 39 E 1% by wt. of Compound of Ex. 6 31 35 F 1% by wt. 01' Compound 01 Ex. 6 31 36 G 1% by wt. of Compound of Ex. 5 27 40 H 1% by wt. of Compound of Ex. 19-.-" 4 27 37 I 1% by wt. of Compound of Ex. 21 5 24 37 1% by wt. oi Compound of Ex. 22 5 27 39 1% by wt. of Compound of Ex. 23-- 5 24 31 1 Since these compounds are water insoluble they were added to the fabric in a separate bath from an isopropyl alcohol solvent after treatment of the fabric with Pad Bath A followed by drying and curing.

Extent of staining Rating points Very heavy (equal to untreated fabric) 0 Heavy (only slightly better than untreated fabric) 1 Moderate (about one-half as intense as untreated fabric) 2 Light (less than one-half as intense as untreated fabric but readily visible) 3 Trace (barely detectable) 4 None 5 Under the above rating system, using the eight stains listed above, a perfect score of 40 (8X5) is obtained if there is no penetration by any of the stains.

Stain release rating (static soils).In this test, the same eight staining materials used in connection with the stain repellancy rating test above are employed. As in the stain repellancy rating test, the fabric is placed on blotting paper and three drops of each stain are dropped onto the fabric from a height of one foot. The stain is allowed to stand one minute and all that has not penetrated is carefully scraped off with a spatula after which the stain impact area is rubbed lightly with a soft paper tissue. The test fabrics, after standing for at least one hour, are then washed under normal laundering conditions (a hot wash followed by a warm rinse in an automatic home laundering machine using 0.25% of a standard household detergent (ALL). The laundered fabrics are then evaluated according to the same rating scale used in determining Stain Repellancy Rating using as the standard for comparison an untreated fabric speciman (no Pad Bath A treatment) which has been stained as described above, but which has not been laundered. According to the above rating system, a perfect score of 40 (8X5) is obtained if all of the stains are completely removed.

Rating data on treated fabric specimens which have been evaluated in accordance with the above tests are shown in Table I. Referring to Example A, which shows the results obtained with no additive in the standard durable press pad bath, it may be seen that very low hydrocarbon repellancy and stain repellancy ratings are obtained, indicating essentially no repellancy characteristics imparted by the durable press pad bath. The stain release rating obtained in Example A shows further that the launderability of the fabrics was quite poor, i.e. most of the stains that entered the fabric were not washed out in the laundering, but were retained on the fabric. In

imparts the high degree of repellancy to the fabric but overcomes the serious problem of stain retention which has been one of the major drawbacks of the durable press treatment. It will be noted that the methylolated derivatives (Examples C through K) gave relatively higher repellancy and stain release ratings than the unmethylolated carbamate used in Example B.

In order to further demonstrate the excellent stain release properties of the compounds of the invention, a second series of tests were run in which the stains were purposely ground into the fabric rather than being dropped on the fabrics with careful removal of the excess which does not penetrate as in the static soil stain release test shown in Table I. In this series of tests, the same standard pad bath formulation (Pad Bath A) was employed and the same type of fabric specimens were padded through the bath and dried and cured under the same conditions as described above in connection with the tests summarized in Table I.

The pieces of test fabric were evaluated for hydrocarbon repellancy rating following the test procedure described above and then were evaluated for stain release with respect to ground in soils according to the following test procedure:

Stain release rating (ground in soils).In this test, the same series of eight staining materials was used as in the stain release test for static soils. Each fabric specimen is placed on blotting paper and three drops of each stain are dropped onto the fabric from a height of one foot. The stain is then ground into the fabric with a spatula, overcoming any repellancy, until the stain penetrates to the blotting paper on the other side. After standing for at least one hour, the stained fabric is washed under normal laundering conditions [hot wash followed by a warm rinse in a standard household automatic washing machine using 0.25% of standard household detergent (A LL)]. After tumble drying the fabric specimens are then evaluated for removal of the stain using the same rating system as described in connection with the stain release rating for static soils.

Table II shows the results of evaluations conducted in the above manner on a series of fabric specimens. In Example L the fabric was treated with the durable press agent only (Pad Bath A) and similar stain repellancy ratings and stain release ratings were obtained as in the previous series of tests (Table I). In Example M a standard commercial fluorocarbon latex produced by the copolymerization of a fiuorinated acrylate with a non-fiuorinated repellancy rating, and the stain release rating actually underwent a substantial increase.

TABLE II Stain Stain Release Pad Beth A Plus Repellancy Rating Rating (Ground in Soils) Example:

L No additive (control) 1 7 Fluorocarbon Latex (1% by wt. of solids)... 26 11 N Fluorocarbon Latex (0.5% by wt. of solids) 27 24 plus 0.5% by wt. Compound 0! Ex. 14.

O 1% by wt. 01' Compound 0! Ex. 1A 8 16 P 1% by wt. of Compound of Ex. 25 Q 1% by wt. of Compouud 01 Ex. 28 R 1% by wt. of Compound of Ex. 30 by wt. 0! Compound of Ex. 30

% by wt. of Compound of Ex. 22

% by wt. of Compound of Ex. 28

% by wt. of Compound oi Ex. 27

% by wt. of Compound 01 Ex. 24

1% by wt. 0! Compound 0! Ex. 26

hydrocarbon monomer, was added to the pad bath in an amount equivalent to 1% by weight of the solids content of the latex. As shown in Table II, the fabric specimen displayed an excellent stain repellancy rating, but a poor stain release rating. That is, although the fabric repelled soils that were dropped on rather than ground into the fabric, the ground in soils were largely retained by the fabric after washing. As can be seen, the fluorocarbon latex treated fabric showed very little improvement in stain release properties over the fabric of Example L containing only the durable press pad bath. In contrast, in Examples N to X inclusive, wheresmall amounts of the compounds of the invention were included, good to excellent repellancy ratings were obtained in each case while at the same time, greatly improved stain release ratings were obtained. That is, even on this drastic test where the soils were purposely ground into the fabric, a high proportion of the soils were removed by one laundering in contrast to the fabrics treated with durable press (Example L) or durable press plus fluorocarbon latex (Example M) where very little of the ground in soils were removed. Example N shows the beneficial effect of incorporating a small amount of a compound of the invention in combination with a fluorocarbon latex. As shown in Table II, the stain release rating in Example N is greatly improved over that in Example M.

The stain repellancy and stain release properties imparted by the compounds of the invention are in many cases retained in large measure after repeated launderings or dry cleanings. Retention of these properties on repeated laundering is particularly characteristic of the methylolated derivatives of the fiuorinated carbamates of the invention, and retention of these properties may be enhanced by use of relatively strong curing agents and curing conditions. A typical pad bath formulation which has been found to promote excellent retention of stain repellancy and stain release properties after repeated launderings is the following: Ingredient Percent by wt.

of pad bath (a) Durable press agent, (1,3-bis(hydroxymethyl)-4,S-dihydroxy-Z-imidazolidinone) (b) Curing agent, zinc chloride 2 (c) Compound of Example 14 1 (d) Water 87 in the tests shown in Tables I and II. After twenty launderings, the fabric still retained most of its initial stain It is understood, of course, that the invention is not limited to the specific embodiments described, which are given for the purpose of illustrating the invention, and that other embodiments not specifically described are included within the scope and spirit of the invention as defined by the appended claims.

We claim:

1. Compounds of the formula 0 Y Ri-( 3-I I-(R O);( JN

where R, is a perfluoroalkyl radical having from 4 to 15 carbon atoms; R is hydrogen, or a lower alkyl radical or a 0 -(RO);( 1N

group; x is an integer from 1 to R is a lower alkylene radical having from two to about 6 carbon atoms; and Y and Z, which may be the same or different, are hydrogen, or a CH OR group where R is hydrogen or a lower alkyl radical.

2. Compounds in accordance with claim 1 in which R; has from 6 to 12 carbon atoms.

3. Compounds in accordance with claim 1 in which R is hydrogen.

4. Compounds in accordance with claim 1 in which x is an integer from 1 to 20.

5. Compounds in accordance with claim 1 in which R is an alkylene group having from two to three carbon atoms.

6. Compounds in accordance with claim 1 in which Y and Z are CH OH groups.

7. Fluorinated carbamates of the formula:

where R; is a perfiuoroalkyl radical having from 4 to 15 carbon atoms, A is hydrogen, a lower alkyl radical or a group, R is a lower alkylene radical having from 2 to about 6 carbon atoms and x is an integer from 1 to 100.

8. Compounds in accordance with claim 7 in which R; contains from 6 to 12 carbon atoms.

9. Compounds in accordance with claim 7 in which A is hydrogen.

10. Compounds in accordance with claim 9 in which x is an integer from 1 to 20.

25 26 11. A compound of the formula: 14. The compound 0 CHZOH ll H I H H II RIC''N(CH2CH20 xC' N\ RzCNOH2CHzOC-NH2 Z 5 and their methylolated derivatives Where R is a perfluowhere R is a perfluoroalkyl group having from 6 to 12 roalkyl group having from 6 to 12 Carbon atoms' carbon atoms; where x is an integer from 1 to 15; and

where Z is hydrogen or the CH OH group. References Cited 12. Compounds in accordance with claim 11 in which UNITED STATES PATENTS x is an integer Of fIOIIl 110 4. 10 2 55 14 951 Olsen 13. The compound H H 0 DANIEL D. HORWITZ, Primary Examiner. R1CN(CH2CH2O)2-H--NH2 US Cl X R and their carbamate-N methylolated derivatives where R 15 is a perfiuoroalkyl group having from 6 to 12 carbon atoms.