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Publication numberUS3684796 A
Publication typeGrant
Publication dateAug 15, 1972
Filing dateFeb 24, 1970
Priority dateFeb 25, 1969
Also published asDE1909273A1
Publication numberUS 3684796 A, US 3684796A, US-A-3684796, US3684796 A, US3684796A
InventorsKlaus-Dieter Muller, Otto Scherer
Original AssigneeHoechst Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Derivatives of bis-perfluoroalkanoyl-phenylene-diamines
US 3684796 A
Abstract
Compounds of the general formula WHEREIN RF and R'F, which are identical or different, represent a perfluorinated alkyl radical having four to 12 carbon atoms, and R1 represents one of the groups AND THEIR USE FOR OIL-, WATER- AND SOIL- REPELLENT FINISHES.
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United States Patent Scherer et a].

[ DERIVATIVES OF BIS- PERFLUOROALKANOYL- PI-[ENYLENE-DIAMINES [7 2] Inventors: Otto Scherer, Bad Soden Taunus;

[22] Filed: Feb. 24, 1970 [21] Appl.No.: 13,752

[30] Foreign Application Priority Data Feb. 25, 1969 Germany ..P 19 09 273.0

[52] US. Cl. ..260/239 E, 8/94.1 R, 8/116.2, 117/1355, 162/158, 260/404, 260/453 AR,

260/471 R, 260/518 A, 260/544 L, 260/544 [51] Int. Cl. ..C07c 119/04, C07d 23/06, C07d 23/08 [58] Field of Search ..260/239 E [56] References Cited UNITED STATES PATENTS 3,250,674 5/1966 Bakeretal. ..260/239 [451 Aug. 15, 1972 Primary Examiner-Alton D. Rollins AttomeyCurtis, Morris & Safl'ord ABSTRACT Compounds of the general formula NH-CO-RF NH--C 04% wherein R and R' which identical or different, represent a perfluorinated alkyl radical having four to 4 12 carbon atoms, and R represents one of the groups and their use for oil-, waterand soilrepellent finishes.

2 Claims, No Drawings DERIVATIVES F BIS-PERFLUOROALKANOYL PHENYLENE-DIAMINES The present invention relates to derivatives of bisperfluoroalkanoyl-phenylene-diamines, more particularly to such of these derivatives which contain an active group in the form of an isocyanate, N,N-ethyleneureidoor N,N-ethylene-amido group at the benzene in which R and R' which may be identical or different, represent a perfluorinated alkyl group having four to 12 carbon atoms and R, represents one of the groups For the application of the compounds of the invention in the production of oil-, waterand soil-repellent finishes, not only the perfluorinated alkyl groups but also the content of isocyanate, N,N-ethylene-ureido or N,N-ethylene-amid0 groups as reactive groups is of importance.

In the preparation of the compounds of the invention, it is suitable to start from derivatives of phenylene-diamine, on the one hand, and from fluorinated carboxylic acids, on the other.

Particularly suitable starting materials are derivatives of m-phenylene-diamine or, preferably, of o-phenylene-diarnine, for example 3,4- or 3,5-diamino-1- nitrobenzene, 3,5- or 3,4-diamino-l-benzoic acid and 3,4- or 3,5-diarnino-benzoic acid methyl ester.

Suitable fluorinated carboxylic acids are compounds of the general formula R COOl-I, in which R represents a perfluorinated alkyl group having four to 12, preferably seven to carbon atoms. As perfluoroalkanoic acids, there may be mentioned by way of example: perfluoro-pentanoic acid, (C F COOH), perfluoro-hexanoic acid (C F COOH), perfluoro-heptanoic acid (C F COOH), perfluoro-octanoic acid (C F, cooh., perfluoro-nonanic acid (C F CO OH), Perfluoro-decanoic acid (C F COOH) or perfluoro-undecanoic acid (C F COOH). For the synthesis, mixtures of the above-mentioned fluorinated carboxylic acids may also be used. With a view to the utilization of the compounds of the invention for the production of oil-, waterand soiLrepellent finishes, perfluoroalkanoic acids containing eight to 11 carbon atoms are preferably used.

The first step in the synthesis of the products of the invention is, preferably, the reaction of the above-mentioned derivatives of mor o-phenylene-diamine with an acid halide, preferably an acid chloride, of the mentioned perfluoro-alkanoic acids. The acid chlorides of the perfluoro-alkanoic acids are obtained in known manner with excellent yields from the respective fluorinated carboxylic acid by reaction with suitable chlorinating agents, for example benzo-tri-chloride. The acylation of the derivatives of 0- or m-phenylene diarnine may be effected either in the presence of a solvent, for example ethyl acetate or chloroform, and of a base, for example dimethylaniline, at temperatures in the range of from about 10 to 50C, or by melting of the starting materials without additives at about to C. The intermediate products thus obtained which, if derivative of o-phenylene-diamine are used, correspond to the formulas (II), (III) and (IV) r moonp r moony utroom ONHCORF @NHCORF NHCORF l N0; 0 OOH 000cm 11 (III) IV can be easily prepared and with good yield by reduction, preferably by hydrogenation under pressure with the use of a catalyst, for example Raney nickel, in the presence of a solvent such as ethanol or ethyl acetate. Hy reaction of the hydrochlorides of these amines (V) with phosgene in an inert solvent, for example benzene, toluene, ethyl acetate, dioxane or chlorobenzene, at an elevated temperature, suitably at about 60 to 120C, the compounds of the invention containing one isocyanate group and corresponding to the formula (VI) NHCORF can be obtained. In a still easier manner and with higher yields, the isocyanates of the formula (VI) can also be prepared by base phosgenisation. In this method, the amine of the formula (V) is introduced at a low temperature, suitably at a temperature in the: range of from about 0 to 20C into a solution of phosgene in an inert solvent and the mixture is slowly heated to a temperature in the range of from 60 to 120C. AFter cooling of the reaction mixture, the crystallized isocyanate can be separated.

By further reacting these compounds which contain one isocyanate group with ethylene imine in a solvent such as ethyl acetate or tetrahydrofurane, suitably at a temperature in the range of from about to 40C, there can be obtained the compounds of the invention which contain one ethylene-urea group and correspond to the formula (VII) ITIIIOORF NIICUR'F CH1 (VII) Such compounds of the invention which contain one N,N-ethylene-amino group can be obtained by preparing,from the bis-acyl-diamindbenzoic acids that correspond to the formula (III) or from bis-acyl-diaminobenzoic acid-methyl esters that correspond to the formula (IV), at first the acid chlorides which, if o-phenylene-diamine is used, correspond to the formula (VIII) ITIHQORF 1 C001 (VIII) For this purpose, the bis-acyl-diaminobenzoic acid methyl esters are previously converted into the free benzoic acids by partial hydrolysis under saponification of the ester group, for example with a mixture of water and acetic acid. The bis-acyl-diamino-benzoic acids can be converted in known manner by reaction with, for example thionyl chloride, into the acid chlorides of the formula (I). From these acid chlorides, there are obtained by further reaction with ethylene imine in the presence of a strong base, for example triethylamine, the compounds of the invention which contain an ethylene-amide group and which, if o-phenylenediamine was used as the starting substance, correspond to the formula (IX) NHCORF CH2 (I The above-described methods for preparing the compounds of the invention are illustrated by the following examples 1 to 6, the percentages being by weight.

EXAMPLE 1 a. Preparation of perfluoro-octanoic acid chloride 1,600 g (8.2 mols) of benzotrichloride were introduced into a glass flask having a capacity of 4 liters and provided with a stirrer, a reflux condenser, a heatable dropping funnel and a thermometer, and heated to 110C. 1,600 g (3.87 mols) of molten perfluoro-octanoic acid were allowed to run in through the dropping funnel,'in the course of 2 hours and while stirring, while maintaining a reaction temperature of about to C. The hydrogen chloride which escaped through the reflux condenser was absorbed in a vessel filled with water. When the addition of perfluoro-octanoic acid was complete, the reaction mixture was heated for 1 hour under reflux.- The aqueous hydrochloric acid obtained by the absorption of hydrogen chloride contained 25 g of dragged-in perfluoro-octanoic acid which was recovered by filtration with suction. The reaction mixture was then distilled over a 40 cm high column packed with Raschig rings. 1,584 g of perfluoro-octanoic acid chloride were obtained; boiling point 136 to 137C. The yield was 96.3 percent, referred to reacted perfluoro-octanoic acid. b. Preparation of 3,4-di-perfluoro-octanoyl-amino-lnitrobenzene 61.2 g (0.40 mol) of 3,4-diamino-l-nitrobenzene, 102 g (0.84 mol) of dimethyl-aniline and 2,000 ml of chloroform were introduced into a glass flask having a capacity of 4 liters and provided with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 364 g (0.84 mol) of the perfluoro-octanoic acid chloride obtained according to (a) were added dropwise, while stirring and cooling, within 1 hour, at a temperature in the range of from 10 to 20C. The whole was further stirred for 3 hours at room temperature. The reaction mixture was then heated for about 5 hours to 50C and subsequently cooled to -18C. 358 g of 3,4-diperfluoro-octanoyl-amino-l-nitrobenzene separated which were filtered off with suction and washed once with chloroform and dried. The product had a melting point of 167 to 170C and was found to be sufficiently pure for the further reaction. The yield was 95 percent, referred to 3 ,4-diamino-1-nitrobenzene. c. Preparation of 3,4-di-perfluoro-octanoyl-amino-laminobenzene A mixture of 290 g (0.307 mol) of the 3,4-di-perfluoro-octanoyl-amino-l-nitrobenzene obtained according to (b), 40 g of wet Raney nickel and 1,000 ml of ethanol were introduced into an autoclave made from stainless steel, having a capacity of 2 liters and provided with a magnetic stirrer. The autoclave was scavenged twice with nitrogen having a pressure of 10 atmospheres gauge, charged with hydrogen having a pressure of 88 atmospheres gauge and then heated to 80C. After 1 hour, the pressure was still 67 atmospheres gauge and did no longer fall in the course of further 8 hours. After cooling, the excess hydrogen was cautiously de-compressed, whereby one part of the magma-like content of the autoclave was dragged with and collected in a separate vessel. The reaction mixture was transferred into a flask provided with reflux condenser and heated to the boiling temperature; during that time so much ethyl acetate was added until the reaction product had passed into solution. After addition of a small amount of active charbon, the solution was filtered hot with suction and the filtrate was cooled to about 0C. The precipitate that had formed, i.e. the 3,4-di-perfluoro-octanoyl-amino-l-aminobenzene was filtered off with suction. By concentrating and cooling the mother liquor, another fraction of the product was recovered. At the whole, 257 g of 3,4-di-perfluoro-octanoyl-arnino-laminobenzene, melting at l76178C,

were obtained. The yield was 91 percent of the theoretical yield.

d. Preparation of aminophenyl-isocyanate 100 g (0.109 mol) of the 3,4-di-perfluoro-octanoylamino-l-aminobenzene obtained according to c),

3,4-di-perfluoro-octanoylsuspended in 1,700 ml of toluene, were introduced into a glass flask having a capacity of 2 liters and provided with a stirrer, a Liebig condenser with vessel, a gas inlet tube with cock and a thermometer. For removing traces of humidity by azeotropic distillation, 200 ml of I toluene were at first distilled off. The Liebig condenser minutes, the whole was filtered hot and the filtrate was a cooled and the precipitate that had separated was filtered off with suction. 80 g of 3,4-di-perfluoro-octanoyl-aminophenyl-isocyanate, melting at 110 to l 12C, were obtained, which could be purified by recrystallization from toluene (melting point l14l 15 C). The yield was 77 percent of the theory.

EXAMPLE 2 Preparation of 3,4-di-perfluoro-octanoyl-amino-l- N,N-ethylene-ureido-benzene 33 g (0.035 mol) of 3,4-di-perfluoro-octanoylamino-phenyl-isocyanate, prepared according to example l, and 100 ml of ethyl acetate were introduced into a glass flask having a capacity of 250 ml and provided with a stirrer, a dropping funnel and a thermometer. A mixture of 1.65 g (0.038 mol) of ethylene-imine, 1 drop of triethylamine and 20 ml of ethyl acetate was added dropwise, in the course of 1 hour, at about C, while stirring and cooling, and the whole was further stirred for hours at to C. A magma-like reaction mixture formed which was filtered off with suction. The residue was washed once with chloroform and dried. 34 g of 3,4-di-perfluoro-octanoylamino-l-N,N-

ethylene-ureido-benzene were obtained.'Melting point:

l-l 5 1C. The yield was 98 percent, referred to the isocyanate initially used.

EXAMPLE 3 tained. Melting point l50-l51C.

b. Preparation of 3,5-di-perfluoro-octanoylamino-lamino-benzene By the same method as that described in example 1 (c), there was obtained, starting from 104 g of 3,5-diperfluoro-octanoylamino-l-nitrobenzene, a total of g (85 percent of the theory) of 3,5-di-perfluoro-octanoylaminol -aminobenzene. Melting point l98-200 C c. Preparation of 3,5-di-perfluoro-octanoylarninophenyl-isocyanate In accordance with the method described in example 1 (d), 50 g of 3,5-di-perfluoro-octanoylamino-laminobenzene were converted into 28 g (54 percent of the theory) of 3,5-di-perfluoro-octanoylamino-phenylisocyanate. Melting point: l03-l 04C.

EXAMPLE 4 a. Preparation of 3,4-di-perfluoro-pentanoylamino-lnitro-benzene By the same method as that described in example 1 (b), there were obtained by reaction of 13.9 g (0.09 mol) of. 3,4-diamino-1-nitrobenzene with 54 g (0.19 mol) of per-fluoropentane-carboxylic acid chloride, prepared according to the method described in example l (a), in the presence of the 23 g (0.19 mol) of dimethylaniline in 200 mlof chloroform as the solvent, 42 g (72 percent of the theory) of 3,4-di-perfluoro-pentanoylamino-l-nitrobenzene. Melting point: l56-l57 O b. Preparation of 3,4-di-perfluoro-pentanoylamino-lamino-benzene In accordance with the method described in example 1 (c), 40 g of 3,4-di-perfluoro-pentanoylaminolnitrobenzene were hydrogenated at 25C with addition of 10 g of moist Raney nickel and 500 ml of ethyl acetate. After removal of the catalyst by filtration with suction, the solvent was removed by distillation and the residue that remained was boiled with chloroform; after having cooled, it was filtered off with suction and dried. 29 g (76 percent of the theory) of 3,4-di-perfluoro-pentanoylamino-l-aminobenzene were obtained. Melting point: l40l43C. c. Preparation of 3,4-di-perfluoro-pentanoylaminophenyl-isocyanate In accordance with the method described in example 1 (d), 26 g of 3,4-di-perfluoro-pentanoylamino-laminobenzene were converted into 22 g (81 percent of the theory) of 3,4-di-perfluoro-pentanoylamino-phenyl-isocyanate. Melting point: 109-1l0 ELE 5 a. Preparation of 3,Ldbperfluoro-octanoylaminobenzoic acid methyl ester 33.2 g (0.20 mol) of 3,4-diamino-benzoic acid methyl ester, 53 g (0.44 mol) of dimethylaniline and 300 ml of ethyl acetate were introduced into a glass flask having a capacity of 1 liter and provided with a stirrer, a dropping funnel and a thermometer. 184 g (0.425 mol) of per-fluoro-octanoic acid chloride were added dropwise in the course of 1 hour, at 10 to 20C, while stirring and cooling. The viscous reaction mass was stirred for 15 hours at room temperature. The reaction product was filtered off with suction and the residue was washed with chloroform and dried. 167 g of 3,4perfluoro-octanoylamino-benzoic acid methyl ester were obtained, corresponding to a yield of 87 percent, referred to the diaminobenzoic acid methyl ester used initially. Melting point: l33-l36C. A pure product having a melting point of -l4lC was ob tained by recrystallization from ethanol.

b. Preparation of 3,4-di-perfluoro-octanoylaminobenzoic acid 201 g (0.20 mol) of the 3,4-di-perfluoro-octanoylamino-benzoic acid methyl ester so obtained, 600 ml of glacial acetic acid and 400 ml of water were heated for 7 hours to 160C in an autoclave made from stainless steel, having a capacity of 2 liters and being provided with a magnetic. stirrer. After cooling, the reaction mixture was filtered off with suction, the residue was washed with water and dried. 150 g of 3,4- di-perfluoro-octanoylamino-benzoic acid, melting point 196198C, were obtained. c. Preparation of 3,4-di-perfluoro-octanoylaminobenzoyl-chloride 50 g (0.053 mol) of 3,4-di-perfluoro-octanoylaminobenzoic acid and 50 g (0.42 mol) of thionyl chloride were boiled for 2 hours under reflux with 250 ml of ethyl acetate and then filtered while hot. The filtrate was evaporated under reduced pressure and the oily residue was stirred with chloroform. The precipitate that had separated was filtered off with suction, washed with chloroform and dried. 42 g (82 percent of the theo y) of 3,4-di-perfluoro-octanoyl-amino-benzoyl chloride were obtained. Melting point: l33-l 36C. d. Preparation of 3,4-di-perfiuoro-octanoylaminobenzoic acid N,N-ethylene-imide 0.95 g (0.022 mol) of ethylene imine, 2.2 g (0.0217 mol) of triethylamine and 50 ml of tetrahydrofurane were introduced into a glass apparatus provided with a stirrer, a dropping funnel and a thermometer. Then, 19.2 g (0.02 mol) of the 3,4di-perfiuoro-octanoylamino-l-benzoyl chloride obtained according to (c), in the form of a solution in 50 m1 of tetrahydrofurane, were added dropwise, in the course of 45 minutes, at a temperature of to +3C, and the whole was stirred for 2 hours. The reaction mixture was then filtered. The filter residue was washed with 25 ml of tetrahydrofurane. From the filtrate, there were ob tained, after evaporation under reduced pressure, 19 g of 3,4-di-perfluoro-octanoylamino-benzoic acid-N,N- ethylene imide. Softening point 70C. The yield was 98 percent of the theory.

EXAMPLE 6 a. Preparation of 3,4-di-perfluoro-alkanoylamino-1- nitrobenzene 8.4 g of a mixture of 4 parts by weight of perfluorononanoic acid chloride, 88 parts by weight of perfluoro-undecanoic acid chloride and about 8 parts by weight of perfluoro-tridecanoic acid chloride were reacted according to the method described in example 1 (b) with 1.0 g of 3,4-diamino-1-nitrobenzene and 1.8 g of diemethyl-aniline in 100 ml of chloroform. 7.2 g of a 3 ,4-di-perfluoro-undecanoylamino- 1 -nitrobenzene mixture which mainly contained perfluoro-undecanoyl radicals were obtained. b. Preparation of 3,4-di-perfluoro-alkanoylamino-lamino-benzene The hydrogenation of 5.0 g of the mixture obtained according to (a) was effected according to the method described in example 1 (c). 4.2 g of a mixture of 3,4-diperfluoro-alkanoyl-amino-l-aminobenzene containing mainly perfluoroundecanoyl radicals were obtained. c Preparation of 3,4-di-perfluoro-alkanoylaminophenyl-isocyanate 4 g of the mixture of 3,4-di-perfluoro-alkanoylamino-l-aminobenzene obtained according to (b) were treated with phosgene according to the method described in example 1 (d). 2.7 g of 3,4-di-perfluoro-alkanoylamino-phenyl-isocyanate mainly containing perfluoro-undecanoyl radicals were obtained. The infrared spectrum showed a sharp strong isocyanate band at 2,293 cm.

The compounds of the present invention permit the production of oil-, waterand soil-repellent finishes which are resistant to washing and to dry cleaning. Substrates onto which these compounds can be applied are natural and synthetic fibers and filaments and any goods prepared therefrom, furthermore leather, paper and similar substances. The oil-, waterand soil-repellent finishes are produced by applying the compounds in the form of aqueous emulsions, sprays or as solutions in organic solvents such as alcohol, chloroform, tetrahydrofurane or, preferably, acetone, onto the substrate to be provided with the finish and removing the solvent, dispersant or propellant by drying. It is of ad vantage to subject the goods subsequently to a heat treatment, preferably at temperatures of more than C.

For the impregnation of textile materials, preferably those compounds of the invention are used which contain an isocyanate group or an ethylene imide group as the active group. The treatment of the textile materials with these compounds not only imparts onto them oiland water-repellent properties, but makes them also insensitive towards oily and aqueous soiling. For example, soilings produced by coffee, wine, sauces and oils on textile materials that are provided with the finish according to the invention can be completely removed by dabbing off with a small piece of cloth. Dirt which has been rubbed into the fabric is completely removed by a treatment with a suitable solvent, for example one of the solvents usually employed in dry cleaning, because the finish produced with the compounds of the invention reduces the capillary action of the textiles to such an extent that the undesired edge formation, which takes place with textile materials that are not provided with a finish, does not occur. The finishes produced according to the invention show a very good resistance to dry cleaning and to washing, especially if they have been subjected for about 1 to 20 minutes to a heat treatment at elevated temperatures, for example to temperatures in the range of from 120 to 170C.

EXAMPLE 7 Table 1 gives examples of the good oil-repellent effects of fabrics that had been treated with the compounds of the present invention. For producing the finishes, specimens of cotton poplin were impregnated with each time 1.0, 0.5, 0.25 and 0.1 percent by weight solutions in acetone of the compounds obtained according to examples 1 (d), 2 and 5 (d), and padded with a squeezing efiect of 100 percent weight increase. The specimens were then dried for 10 minutes at 1 10C and heated for 5 minutes to C. The finishes produced on the fabric were thus 1,0, 0.5 0.25 and 0.1 percent by weight.

The oil-repellent properties of the specimens finished were evaluated according to the test method described in the Textile Research Journal, Vol. 32,

(1962), pp. 320 to 331. In this test, the resistance ofa fabric to wetting by oils is measured. Parafiin oil DAB 6 and mixtures of paraffin oil with n-heptane are used as test oils. The admixture of n-heptane to the paraffin oil increases the wetting effect of the oil mixture. The different test oil mixtures are applied in the form of a drop onto the fabric to be tested and allowed to act on it for 3 minutes. Then, the specimen is given that oil-repellent value which corresponds to the test oil mixture which still does not wet the fabric. The oil-repellent value of the fabric to be tested is the higher the larger the proportion of n-heptane in the test oil mixture which just still does not yet wet.

The values of the oil-repellent effect (resistance to wetting) are the sum of 50 and the proportion, in percent by volume, of n-heptane in the text mixture, according to the following evaluation key:

Resistance to by volume 96 by volume wetting of n-heptane of by oil paraffin oil TABLE 1 Product according Oil-repellent effects with to Example finishes of 1.0% by 0.5% by 0.25% by 0.1% by weight weight weight weight l.d) 120 120 80 2. 120 110 100 5.d) 120 110 1 10 90 The fabrics provided with a finish also showed good water-repellent effects. The specimens were not wetted within 3 minutes by an applied drop of water.

EXAMPLE 8 Specimens of A. cotton poplin and of B. a mixed fabric of 50 parts of polyethylene glycol terephthalate and 50 parts of cotton,

were impregnated with an acetone solution containing 1 percent by weight of the compound obtained according to example 1 (d) and padded with a squeezing effect to obtain a weight increase of 100 percent. The specimens were then heated for 5 minutes to 150C.

The oil repellent properties of the fabrics so provided with a finish were then evaluated with the aid of the test method described in example 7, first directly after treatment, then after having subjected the fabrics to washing once, and then twice, and once to dry clean-- ing. The results are shown in table 2.

Furthermore, the water-repellent properties of the fabric specimens so finished were tested in accordance with the Spray-test according to AATCC 22-1952. Values of 100 were obtained in all cases.

' l 0 The washing of the specimens was efiected for 20 minutes at 60C with 2 g of detergent per liter of water and a goods to liquor ratio of 1:30 in a laboratory washing machine (Linitest apparatus).

The dry cleaning was effected with the aid of carbon tetrachloride for 15 minutes at room temperature.

A. cotton poplin and of B. a mixed fabric of 50 parts of polyethylene glycol terephthalate and 50 parts of cotton,

were treated uniformly with a spray containing 40 percent of a mixture of 10 parts by weight of fluorotn'chloromethane and 90 parts by weight of difluoro-dichloromethane as propellant and 40 parts by weight of a solution of 0.5 part by weight of the compound obtained according to example 5 (d), 39.5 parts by weight of acetone and 60.0 parts by weight of 1,1 ,1- trichloroethane. After spraying, the specimens of fabric were dried at room temperature. The quantity applied was about 1 percent by weight.

The fabric specimens were tested for their oil-repellent properties according to the test method described in example 7, directly, then after having been subjected once and twice to washing and once to dry cleaning.

Washing and dry cleaning of the specimens was effected in accordance with the indications given in example 8.

The results of the tests are shown in table 3.

TABLE 3 Substrate Oil-repellent Oil-repellent effect after effect 1st 2nd Dry washing washing cleaning A 1 10 1 l0 1 10 B 130 120 1 l0 1 10 The test for the water-repellent properties of the specimens gave good water repellent values for all specimens.

EXAMPLE 10 A 0.5 percent emulsion of the 3,4-di-perfluoro-octanoylamino-l-N,N-ethylene-ureidobenzene obtained according to example 2 was prepared. For this purpose, the quantity of water required for preparing a 0.5 percent emulsion was stirred into a 2.5 percent solution of this product in acetone, with addition of the sodium salt of perfluoro-octanoic acid as emulsifier in a quantity of 10 percent, referred to the quantity of product initially used.

The emulsions obtained were stable over a prolonged period of time and could be combined in excellent manner with other products conventionally used for high quality finishes.

11 l2 Specimens of In addition, all of the finished fabrics exhibited good A. cotton poplin and of water repellent properties. B. a mixed fabric of 50 parts of polyethylene glycol We claim: terephthalate and 50 parts of cotton were impregnated 1. A compound of the formula with the emulsion and squeezed to a weight increase of 5 100 percent. The specimens were dried for minutes at 1 10C and then after-heated for 5 minutes to 150C.

The test for the oil-repellent properties of the fabric NHCORF specimens according to the method described in example 7 was carried out directly after the treatment, after 10 on one and after two washings and after one dry cleaning. 2 Washing and dry cleaning of the fabrics was effected in NH CO N accordance with the indications given in example 8. CH2 The results of the tests are shown in Table 4.

TABLE 4 wherein R and R which are identical or different, represent a perfluorinated alkyl of four to 12 carbon Fabric Oil-repellent Oil-repellent effect afier atoms Swashmg 2. 3,4-di-perfluoro-octanoyl-amino-1-N,N-ethylene- A 120 100 90 ureido-benzene. B 130 120 120

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3250674 *Apr 22, 1965May 10, 1966Stauffer Chemical CoMethod for controlling insects
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4537594 *Jul 13, 1984Aug 27, 1985Fogarty P.L.C.Processed feathers
Classifications
U.S. Classification548/966, 554/58, 564/155, 8/191, 560/19, 562/450, 562/863, 562/449, 560/358, 162/158, 554/56, 8/181, 562/862, 8/94.10R, 562/840, 8/194, 554/57
International ClassificationC07D203/16, D06M13/408, C07C233/00, C07D203/20, C07D203/18, C07C51/60, C07C265/12
Cooperative ClassificationC07D203/18, D06M13/408, C07C51/60, C07D203/20, C07C265/12
European ClassificationC07C265/12, C07C51/60, C07D203/18, D06M13/408, C07D203/20