3,238,235 United States Patent Office Patented Mar. 1, 1966

1. 2 3,238,235 FLUORNATED AMIDO CARBOXYLIC ACDS CF3IC Flic-N-CH.C-OH AND SALTS THEREOF Murray Hauptschein, Glenside, and Sameeh S. Toukan, Levittown, Pa., assignors to Pennsalt Chemicals Corpo 5 ration, Philadelphia, Pa., a corporation of Pennsylvania CFC Flic-N-CH-C-OH No Drawing. Filed Apr. 29, 1963, Ser. No. 276,160 12 Claims. (C. 260-404) CFC Full-N-CHé OH This invention relates to fluorinated compounds having O valuable surface properties and more specifically is con CF3 O O cerned with certain new derivatives of long chain per CFCFC Flic-N-CHCHC OH fluorinated carboxylic acids which possess such surface properties in a particularly high degree. (F. O It is known that relatively long chain perfluorinated 15 CFCFCFal -N-CH,OH,C OH carboxylic acids and salts thereof, e.g. perfluorooctanoic acid and its ammonium and metal salts, have unusual (F. O Surface properties. They are known for example to CFCFCF -N-CHCHé OH reduce the surface tension of aqueous systems to un usually low values and thus have valuable uses as ultra 20 O O performance surfactants in such systems. According to CF (CFle C -N-CHCH, O this invention, certain new derivatives of certain high members of such acids have been found to display sur F. face properties which are superior in a marked and 'sur CF, CFCFC-N-CEIC OF prising degree to the acids themselves, to the salts of 25 Hs such acids, as well as to compounds of similar types derived from perfluorinated sulfonic acids. (F 9 The new compounds of the invention may be repre CFaCFCF); C-N-CBC OEI sented by the general formula 3 30 O O CF3 O C.F.-N-R-E-OM CFCFC Flic-N-OH.c OE CH3 where CFan1 is a perfluoroalkyl group which may have O O a straight or branched chain and which has a chain 35 CFC File-N-ch, OH length of at least seven carbon atoms; where n is an CH3 integer having a value ranging from 8 to 13; where R is CF3 O O hydrogen or an alkyl group (which may be straight or - branched) having from 1 to 4 carbon atoms; where R' CFCFC F.C-N-H OE is an alkylene radical or a monohydroxyalkylene radical 40 CH3 (which may be straight or branched) having from 1 to 6 carbon atoms and where M is hydrogen, an alkali metal F. ( ) or ammonium. CFCFC FC-N-Hc OH Of particular value are compounds of the above type CH3 where the perfluoroalkyl group C, Fani contains from 45 O O 10 to 12 carbon atoms. Despite the very low solubility - || of such compounds in aqueous systems they display re CF3IC Flac-N-Hc OE markably superior surface properties when employed in CE such systems. Of particular value also are compounds of CF3 O O the above type where R is hydrogen or an alkyl group 50 C Fé FC Flt-N-OH, OE containing from 1 to 2 carbon atoms; and those in which &H, R’ is an alkylene radical having from 1 to 3 carbon atoms. Typical examples of the new compounds of the inven CF3 O O C FéHIC Flé-N-OH, OE tion shown in the form of the free acid are the following: 55 &H, F. O O CF3 CFCFls -N-CH-C-OH CFC Flé-N-OH, oh (F 9 60 &H, CF3 CFC Flic-N-CH-C-OH CF's O O F. C Fé FC Fil-N-CHCHCH.) OE CFCFC Fé-N-CHé-OH &H, 3,238,235 4. acid halide or a perfluorinated halosulfate with a primary - CF3. . . . O Chion amine. The amide thus produced is then reacted with CF.CFCF-C-N-CH-COH metallic sodium in an organic solvent such as toluene to form a sodium derivative which is then reacted with a CIN CH, chloro or bromo ester to form an ester derivative which CF3 CH O is then hydrolyzed to provide the desired end product. CF.CFCF-C-N-CH-coh| || This method may be illustrated by the preparation of ce CH, 0 cificNCH.cooH pH C2H starting with the chlorosulfate CFOSOCl in accordance F. H, 9 with the following: CF.CFCF-C-N-CH-coh (a) The new compounds of the invention may be prepared 5 CgF19 OSOC - 3C2H5NH2 --> O by the direct reaction of the acid fluoride or the acid | chloride of a perfluorinated carboxylic acid of the proper CsF17 CNBC2H5 -- C2H5NEISONHCH -- HCl +2HF chain length with an amino acid. This reaction may be (b) O O illustrated by the reaction of perfluorononanoic acid toluene fluoride with glycine in accordance with the following: 20 CsF17 CNHCH5 -- Na - C6F1, CN (Na) CH (c) O (diethylene glycol O O | dinnethyl ether) cifier -- NH2CH2COOH --> CF&NHCHCOOH + HF CslF 17 CN (Na) C2H5 -- BrCHCOO CEI - - - - - The reaction is preferably carried out by dissolving or suspending the perfluoro acid fluoride in an anhydrous 25 cificNCHC OOC2H Solvent and mixing the solution slowly with a suspension CH5 of the amino acid in the same solvent and then refluxing (d) O mild alkaline hydrolysis (NaOH) the mixture for several hours. The amino acid may be CsF17CNCF2COO CEI5 - - - - added slowly to the perfluoro acid fluoride or conversely, 30 2H5 the acid fluoride may be added slowly to the amino acid. O O The reaction mixture is filtered to remove insoluble ma acidification terial which generally includes excess amino acid and its circNCH.cooN --> CSF1, CNCHCOOE hydrogen fluoride salt, after which the amide product CEis Hs may be isolated by evaporation of the solvent and purified 35 After preparation of the free acid as described above, if necessary by crystallization, or similar techniques. the alkali metal salts such as the ammonium salt, potas Suitable anhydrous solvents include e.g. diethylether, di sium salt, Sodium salt, lithium salt, etc. may be readily methoxyethane, CHOCH2CHOCH, tetrahydrofuran, prepared, preferably by dissolving the free acid in a sol trichlorotrifluoroethane and benzene. Reaction tempera vent such as isopropanol, ethanol or methanol, and titrat tures of from 0° C. to 150° C. and more usually from 20 40 ing the solution to its equivalence point with a solution of C. to 100 C. will generally be used. Sufficient amino acid the alkali metal hydroxide preferably in a solvent such is employed to insure high conversion of the perfluoro as ethanol, methanol, or an aqueous alcoholic solution. acid fluoride, molar ratios of the amino acid to the per The salt is readily recovered by evaporation of the solvent fluoro acid fluoride of from 1:1 to about 3:1 being gen and drying at a temperature range of 40-80 C. erally preferred. Reaction may be generally carried out The ammonium salt may be readily prepared by pass most conveniently at atmospheric pressure and reaction ing ammonia gas through a solution of the free acid in a times of from about 10 minutes to 10 hours are generally Solvent such as diethyl ether, methanol, isopropanol, satisfactory. CF2CCFCl2 or acetone, after which the solvent is evap The compounds of the invention may also be prepared orated to recover the ammonium salt. by the direct reaction of an amino acid with a perfluoro 50 The perfluorinated carboxylic acid fluorides used to pre inated halosulfate of the formula CF2n OSOZ where n pare the compounds of the invention may be obtained is an integer ranging from 9 to 14 and where Z is chlorine in a variety of ways. Perfluorinated acid fluorides con or fluorine. This method may be illustrated by the reac taining up to 10 carbon atoms may be prepared by the tion of perfluorononyl chlorosulfate with glycine in ac electrochemical fluorination of the corresponding hydro cordance with the following: carbon carboxylic acid in liquid hydrogen fluoride as O described for example in U.S. Patent 2,519,983 of Simons. CF190SO2Cl -- 3NH2CH2COOH -> C.F. bNHCHCOOH The perfluorinated acid fluorides may also be obtained by the reaction of perfluorinated iodides with fuming sulfuric - HOOCCHNHSONHCHCOOH -- 2HF -- HCl acid as described in co-pending application Serial No. This reaction is carried out preferably by dissolving or 60 212,137, filed July 24, 1962, now abandoned, of Murray suspending the perfluoroinated halosulfate in an anhy Hauptschein and Chester L. Parris for Preparation of drous solvent and the solution then mixed with a sus Fluorinated Organic Compounds. The fluorinated iodide. pension of the amino acid in the same solvent followed precursors may be prepared by telomerization procedures. by refluxing for sufficient time to insure complete reac Such as by the reaction of perfluoroisopropyl iodide. tion. Insoluble material is then removed by filtration after (CFa)CFI or perfluoroethyl iodide CFCFI with tetra which the crude product is isolated by evaporation of the fluoroethylene to produce telomers of the formula solvent followed sometimes by recrystallization. (CF3)2CFICFCFal. I and CFCFCFCFI If desired a tertiary amine, e.g. triethylamine or pyridine respectively. may be added to the reaction mixture in either of the The perfluoroinated chlorosulfates or fluorosulfates may 70 be prepared by the reaction of perfluorinated iodides with above methods of synthesis to act as a scavenger for the chlorosulfonic or fluorosulfonic acid following the proce hydrogen halide liberated during the reaction. dures described in detail in co-pending application Serial Another less preferred procedure for the preparation of No. 735,702, filed May 16, 1958, now abandoned, of the compounds of the invention involves the initial Murray Hauptschein and Milton Braid for Halogenated preparation of an amide by the reaction of a perfluorinated 5 Organic Compounds. 3,238,235 5 6 Examples of suitable amino acids useful for preparing product N-perfluoro(9 - methyldecanoyl)aminoacetic the compounds of the invention are the following: acid, glycine------NH2CH3COOH Palanine------NECH2CH2COOH CFCF(F (CF). CNHCH2COH Sarcosine------HN-ch.cooh 5 Analysis, calculated for CHFNO3: C, 25.1; H, 0.65; CH3 N, 2.25; molecular weight, 621. Found: C, 25.1; H, CH3 - 0.38; N, 2.14; molecular weight (neutralization equiva lent), 616. The infrared spectrum of this compound alanine------NH&H cooH. shows strong bands at 5.82u and 6.43p, characteristic of (Hon 0. a secondary amide. Serine------n ... m ...... n w w a m NEHCCHCOOH Example 3-Preparation of potassium N-perfluoro 1-aminobutyric acid.------NHCHCH2CHCOOH (9-methyldecanoyl)aminoacetate The potassium salt of the acid ce CH oH, 5 valine------NH&H-C O OE CF3 CFF. (CF). ()CNHCHCOOH ot CH3 is prepared by dissolving the acid in a large excess of isopropanol and then titrating this solution to equivalence C 20 point with a 0.5 N potassium hydroxide in ethanol solu H. tion. The solution is evaporated to dryness at a tem Leucine------NH-CH-C-OH perature up to 80 C. and then dried in a vacuum desic The following examples, illustrate the preparation of cator at 40° C. to provide the potassium salt the new compounds of the invention. 25 Example 1.-Preparation of perfluoro(9-methyldecanoyl CFCFF. (CF). CNHCH2COK fluoride a white crystalline solid. A 1400 milliliter stainless steel autoclave is charged Example 4.-Preparation of sodium N-perfluoro(9- with 900 grams of fuming sulfuric acid ( 35% by weight 30 methyldecanoyl)aminoacetate of SO) and 278 grams (0.4 mole) of perfluoro(9-meth yldecyl iodide, ICFICFICFals. The autoclave is Following a procedure similar to that described in Ex sealed and heated with shaking at 145-155 C. for 16 ample 3 except that a 0.5 N sodium hydroxide in ethanol hours, after which it is cooled to room temperature, open solution is used instead of the potassium hydroxide solu ed, and the contents transferred to a separatory funnel 35 tion, the sodium salt while carefully excluding moisture from the product. CF8 O The reaction mixture separates cleanly into a lower Sul furic acid phase and an upper organic phase. Upon care créf (CF&NHCH, CoNa ful separation of the two phases, 228 grams of organic a white crystalline solid is obtained. material is collected and vacuum distilled. There is ob- 40 Example 5-Preparation of ammonium N-perfluoro tained 178.4 grams (80% yield) of the acid fluoride (9-methyldecanoyl)aminoacetate CFCFCFCOF having a boiling point of 81 at 30 mm. Hg, and 43.2 grams (19% yield) of the perfluori The acid nated acid (CFCFCFCOOH, M.P. 61-64° C. and a product hydrolyzable thereto, and only about 3 grams 45 CFCF(F (CF&NHCH.co 9 OH (1%) of unreacted iodide. The infrared spectrum of the is dissolved in a large excess of ethyl ether. Ammonia acid fluoride shows a characteristic strong peak at 5.30p. gas is bubbled through the solution at room temperature while the carboxylic acid shows characteristic strong until precipitation is complete. The ether solvent is re bands in the infrared spectrum at 3.20u, 5.62u, and 6.95u. moved by evaporation under vacuum to provide the am Example 2-Preparation of N-perfluoro(9-methyl- 50 monium salt decanoyl)aminoacetic acid F. To a stirred suspension of 7.50 grams (0.10 mole) of CFCF (CF). CNHCHCONH glycine, NHCHCOOH, in 70 milliliters of anhydrous di a white crystalline solid. methoxyethane there is slowly added a solution of 11.30 55 Example 6.-Preparation of perfluoro(7-methyl grams (0.02 mole) of octanoyl fluoride (F 9 A 1400 milliliter stainless steel autoclave is charged CFCF (CF), CF with 292 grams (0.49 mole) of perfluoro(7-methyloctyl in 30 milliliters of anhydrous dimethoxyethane. This 60 iodide, CFCFECFI and 900 grams of fuming sul mixture is refluxed under nitrogen for 4 hours at atmos furic acid (35% by weight SO3). The autoclave is sealed pheric pressure (reflux temperature approximately 85 and heated with shaking at 134-143° C. for 16 hours. C.). The reaction mixture is filtered to remove 6 grams The autoclave is cooled and the contents transferred to a of insoluble material and the solvent of the filtrate is re Separatory funnel while carefully excluding moisture from moved by distillation in vacuo at a bath temperature of 65 the product. The reaction mixture separates cleanly into 50-60° C. The residue is extracted with three 50 milli a lower Sulfuric acid phase and an upper organic phase. liter portions of diethyl ether. The ether extract is de Upon careful separation of the two phases 227 grams of canted from the residue, washed with about 150 milli organic product is collected and vacuum distilled. There liters of water, dried with anhydrous magnesium sulfate is obtained 155.4 grams (73.8% yield) of the acid fluo and evaporated on steam bath to give 11.2 grams (90% 70 ride (CF)2CFICF).5COF having a boiling point of 70° yield) of a liquid residue which rapidly solidifies on stand C. at 80 mm. Hg, 46.5 grams (21.8% yield) of the per ing at room temperature. Upon recrystallization of this fluorocarboxylic acid (CFCFCFCOOH and a product from a mixture of benzene and ethyl acetate in product hydrolyzable thereto and 22 grams of unreacted the ratio of 9:1 there is obtained a white crystalline solid iodide. The total yield of perfluoro acid fluoride plus having a melting point of 130-131 C., this being the 75 perfluoro acid is 95.6%. The infrared spectrum of the 3,238,235 7 3. acid fluoride shows a characteristic strong band at 5.30p. is reacted with glycine in a molar ratio of acid fluoride to while the carboxylic acid shows characteristic strong glycine of 1:5 in refluxing dimethoxyethane for 5 hours. bands at 3.20a, 5.62u, and 6.95u. From this reaction mixture an 80% yield of a white Example 7-Preparation of perfluoro(7-methyl crystalline solid, octanoyl) fluoride CF3 Following the procedures of Example 6, 292 grams of CFCF (cr.) (NHCH-cooli iodide ICFCFCF) is reacted with 900 grams of having a melting point of 148-149 C. is obtained. Anal fuming sulfuric acid (35% SO3 by weight) at a tempera ysis, calculated for CHFNOs: C, 25.0; H, 0.56; N, ture of 132-138 C. for 8 hours. There is obtained 253 1.94: molecular weight, 721. Found: C, 25.0; H, 0.43; grams of organic product which is vacuum distilled to 10 N, 2.00; molecular weight (neutralization equivalent), provide 154 grams of unreacted iodide and 93.2 grams of 728. The infrared spectrum of this compound displays product, 92% of which is the acid fluoride strong bands at 5.82u and 6.42u. The potassium, sodium and ammonium salts of the (CF) CF (CF)COF above acid are prepared following the procedures of Ex and 8% is the carboxylic acid (CF)CF (CF)COOH amples 3, 4 and 5 respectively. These salts are white and a product hydrolyzable thereto. crystalline solids. Example 8-Preparation of N-perfluoro(7- Example 11-Preparation of N-perfluoro(7- methyloctanoyl)aminoacetic acid methyloctanoyl)-3-aminopropionic acid 20 To a stirred suspension of 7.50 grams (0.10 mole) of To a stirred suspension of 8.90 grams (0.10 mole) of glycine in 70 milliliters of anhydrous diethyl ether there f3-aminopropionic acid, NH2CHCHCOOH, in 70 ml. of is slowly added a solution of 9.70 grams (0.021 mole) of anhydrous diethyl ether there is added slowly a solution of 11.60 grams (0.025 mole) of CFCF(r. (CF), CF9 25 in 30 milliliters of anhydrous diethyl ether. The mixture is refluxed under nitrogen for 6/2 hours at atmospheric in 30 milliliters of anhydrous diethyl ether. This mixture pressure (reflux temperature about 35° C.). The reac is refluxed under nitrogen for 3 hours at atmospheric pres tion mixture is filtered to remove 6.3 grams of insoluble 30 Sure (reflux temperature about 35° C.). The reaction material. The filtrate is concentrated on a steam bath to mixture is filtered to remove 10 grams of insoluble ma provide 10 grams (92% yield) of a white solid residue. terial and the filtrate dried with anhydrous magnesium After recrystallization from benzene there is obtained a Sulfate and then evaporated on a steam bath. There is ob white crystalline product having a melting point of 97.5- tained 10.70 grams (80% yield) of a liquid residue which 99 C., this being the amido acid 35 Solidifies quickly on standing at room temperature. Re crystallization of this material from benzene gives a white SF ( ) crystalline solid having a melting point of 88.5-90° C. CF3 CF (CF). CNHCH2COH and having the structure: Analysis, calculated for CHF1NO3: C, 25.4; H, 0.77; N, 2.69; molecular weight, 521. Found: C, 25.5; H, 1.05; 40 F. N, 2.62; molecular weight (neutralization equivalent) CF3 CFCFls CNHCHCHCOOH 516. The infrared spectrum of this compound displays strong bands at 5.83p, and 6.47p. Analysis, calculated for C12HFNOs: C, 26.9; H, 1.13; The potassium salt, sodium salt and the ammonium salt N, 2.62; molecular weight, 535. Found: C, 27.2; H, 1.27; of this acid are prepared by the methods set forth in Ex N, 2.70; molecular weight (neutralization equivalent), 45 529. The infrared spectrum of this compound displays amples 3, 4 and 5 respectively. These salts are white Strong bands at 5.87u, and 6.44 u. crystalline solids. The potassium, sodium and ammonium salts of the Example 9-Preparation of perfluoroll above acid are prepared following the procedures de methyldodecanoyl fluoride Scribed in Examples 3, 4 and 5 respectively. These salts A 1400 milliliter stainless steel autoclave is charged with 50 are white crystalline materials. 318.4 grams (0.4 mole) of perfluoro(11-methyldodecyl Example 12-Preparation of N-perfluoro(9- iodide and 900 grams of fuming sulfuric acid (35% SO3). methyldecanoyl)-3-aminopropionic acid The autoclave is sealed and heated with shaking at 160 165 C. for 16 hours. The autoclave is cooled and opened Following the procedures described in Example 2, the whereupon the organic product solidifies, permitting the 55 perfluorinated acid fluoride spent sulfuric acid to be decanted off, after which the F. organic product weighing 252.5 grams is removed from CFCF (CF), CF the autoclave. Upon vacuum distillation of the organic product there is obtained 104 grams (58.1% yield) of the is reacted with (3-aminopropionic acid in a ratio of acid acid fluoride ICF)2CFICF2)9COF having a boiling point 60 fluoride to the amino acid of 1:5 in refluxing anhydrous of 88° C. at 7 mm. Hg, 33.0 grams (18.5% yield) of the dimethoxyethane for 6 hours. From this reaction mixture perfluorocarboxylic acid (CFalCFICFJgCOOH having there is obtained a 79% yield of a white crystalline solid a melting point of 88-89° C. together with 105 grams of unreacted iodide. The infrared spectrum of the acid F. fluoride shows a characteristic strong band at 5.30p, while 65 CF3 CF (CF2), CNHCHCHCOOH the carboxylic acid shows characteristic strong bands at having a melting point of 116-117° C. Analysis, cal 3.20 u, 5.62u and 6.95u. culated for C14HFaNO3: C, 26.5; H, 0.95; N, 2.20; molecular weight, 635. Found: C, 26.5; H, 1.19; N, 2.18; Example 10-Preparation of N-perfluoro(11 molecular weight (neutralization equivalent), 630. The methyldodecanoyl)aminoacetic acid 70 infrared spectrum of this compound displays strong bands Following the procedures of Example 2, the perfluo at 5.82u, and 6.41 u. rinated acid fluoride The potassium, Sodium and ammonium salts of the above acid are prepared according to the methods de (F. O Scribed in Examples 3, 4 and 5 respectively. These salts créf (crer are white crystalline solids. 3,238,235 9 10 Example 13-Preparation of N-perfluoro(11-methyl dimethoxyethane for 8 hours. From this reaction there dodecanoyl)-3-amino-propionic acid. is obtained a 60% yield of a white crystalline solid Following the procedures described in Example 2, the acid fluoride F. : F. CFCF (C F&N-chic O OE CFCF (CF) CF CH is reacted with 6-aminopropionic acid in a ratio of the melting at 88.5-90° C. Analysis, calculated for acid fluoride to the amino acid of 1:5 in refluxing di C14HFaNO3 methoxyethane for 6 hours. From this reaction there C,26.5; H, 0.95; N, 2.20; molecular weight, 635. Found: is obtained a 71% yield of a white crystalline solid O C, 26.8; H, 1.12; N, 2.22; molecular weight (neutraliza product tion equivalent), 635. The infrared spectrum of this CF3. O . compound displays strong bands at 5.70u and 6.00a. CFCF (CF). CNHCHCHCOOH The potassium, sodium and ammonium salts of the 5 above. acid are prepared following the procedures of having a melting point of 138-140°C. Analysis, cal Examples 3, 4 and 5 respectively. These salts are white culated for CHFNOs: C, 26.1; H, 0.82; N, 1.91; crystalline solids. molecular weight, 735. Found: C, 26.3; H, 0.78; N, 1.96; molecular weight (neutralization equivalent), 730. The Example 16-Preparation of N-methyl-N-perfluoro infrared spectrum of this compound displays strong (11-methyldodecanoyl) aminoacetic acid bands at 5.85u and 6.43a. 20 The potassium, sodium and ammonium salts of the Following the procedures of Example 14, the per above acid are prepared following the procedures de fluorinated acid fluoride scribed in Examples 3, 4 and 5 respectively. These salts are white crystalline solids. 25 CF3 CFF (CF)CF Example 14-Preparation of N-methyl-N-perfluoro(7- is reacted with sarcosine CH3NHCHCOOH in a molar methyloctanoyl)-aminoacetic acid. ratio of acid fluoride to sarcosine of about 1:5 in reflux To a stirred suspension of 11.60 grams (0.025 mole) ing dimethoxyethane for 6% hours. There is obtained of sarcosine, 30 from this reaction a 68% yield of the product HN-CECOOH &H, CFa in 70 milliliters of anhydrous dimethoxyethane there is cFéF (CP).cN–Chicoot gradually added a solution of 8.90 grams (0.1 mole) of CH3. the acid fluoride 35 a White crystalline solid having a melting point of 105 CF3 O 107 C. Analysis, calculated for C18HsFasNOs: C, ord F (CF). F 26.1; H, 0.82; N, 1.91; molecular weight, 735. Found: in 30 milliliters of anhydrous dimethoxyethane. This C, 25.9; H, 0.72; N, 1.99; molecular weight (neutraliza mixture is refluxed under nitrogen for 3 hours at at 40 tion equivalent), 733. The infrared spectrum of this mospheric pressure (reflux temperature of about 85°C.). compound displays strong bands at 5.70, and 6.01u. The reaction mixture is then filtered to remove 7.5 grams The potassium, sodium and ammonium salts of the of insoluble material, and the filtrate distilled under above acid are prepared following the procedures of vacuum to remove the solvent. To the residue is added Examples. 3, 4 and 5 respectively. These salts are white 50 milliliters of diethyl ether and the mixture is washed 45 crystalline solids. with water. The ether layer is then dried with anhy drous magnesium sulfate and evaporated on a steam bath Example 17-Preparation of N-perfluoro(9-methyl to give 11.4 g. (85% yield) of a liquid residue which decanoyl)) aminoacetic acid rapidly solidifies on standing at room temperature. Re This example illustrates, an alternative procedure for crystallization of this product from benzene gives a 50 the preparation of the compounds of the invention by white crystalline product having a melting point of 67.5- sign of an amino acid with a perfluorinated chloro 69°C, consisting of the product Sulfate. A solution of 19.7 grams (0.029 mole) of perfluoro (F. (9-methyldecyl) chlorosulfate, CFCF (C F.CN-chic OOH 55 C3 CF Analysis, calculated for C12HF1NO3: C, 26.9; H, 1.13; cFéric FlsOSOCl N, 2.62; molecular weight, 535. Found: C, 26.9; H, in 30 milliliters of anhydrous diethyl ether is added drop 1.01; N, 2.63; molecular weight (neutralization equiva by drop to a stirred suspension of 22.5 grams (0.3 mole) lent), 526. The infrared spectrum of the compound 60 of glycine, NH2CHCOOH, in 120 milliliters of anhy displays strong bands at 5.74u and 5.91p. drous diethyl ether. The mixture is refluxed under ni The potassium, sodium and ammonium salts of the trogen for 6 hours after which the reaction mixture is above acid are prepared in accordance with the pro filtered to remove 21.8 grams of insoluble material and cedures described in Examples 3, 4 and 5 respectively. the filtrate is then washed with water, dried with anhy The salts are white crystalline solids. 65 drous magnesium Sulfate, and evaporated on a steam bath to give 14 grams (78% yield) of a liquid residue which Example 15.-Preparation of N-methyl-N-perfluoro rapidly solidifies on standing at room temperature. Re (9-methyldecanoyl) aminoacetic acid crystallization of this product from a mixture of benzene Following the procedures of Example, 14, the perflu and ethyl acetate in the ratio of 9:1 provides a white orinated acid fluoride 70 crystalline solid having a melting point of 130-130 C. CF3 O consisting of N-perfluoro-(9-methyldecanoyl) amino CFCF (CF), CF acetic acid, is reacted with sarcosine CH3NHCHCOOH, in a molar CF, O ratio of acid fluoride to sarcosine of 1:5 in refluxing 75 CFCFC F&NHCH.co OH 3,238,235 2 Example 18-Preparation of N-ethyl-Nperfluoro-(9- (c) Hydrolysis of methyldecanoyl) aminoacetic acid This example illustrates another alternative procedure F. for the preparation of the compounds of the invention. CFCF (CFron-CH.cooch, (a) Preparation of CH CF O A mixture of 5 grams of the ester and 15 milliliters of CFCF (CF), C-NHCH 50% aqueous ethanol containing 0.6 gram of sodium Into a stirred ice-cold solution of 523.5 grams (0.76 hydroxide is shaken for 15 minutes until a clear one mole of O phase solution is obtained. The solution is cooled in ice Water, acidified with concentrated sulfuric acid after (F. which 10 milliliters of water is added and the mixture CF3 CF (CF)3OSOCI shaken. An insoluble material forms which is extracted in 600 milliliters of anhydrous diethyl ether there is with diethyl ether. The ether solution is dried and bubbled ethylamine gas over a period 7 hours. The mix evaporated on a steam bath leaving a liquid residue is filtered to remove insoluble material and the filtrate re which solidifies upon drying overnight under reduced move insoluble material and the filtrate refluxed for 3 pressure. There is obtained 4.5 grams (93% yield) of hours. The reaction mixture is then washed with the product N-ethyl-N-perfluoro(9-methyldecanoyl) water, a water insoluble gel forms which after treatment with a large excess of isopropyl ether separates into 20 aminoacetic acid, two layers, an ether layer and an aqueous layer. The ether layer is dried and decolorized; the ether is evapo CF. rated leaving a brown liquid residue which is distilled in CFCF (C F.CN–Chico OE vacuo to give a colorless oily liquid which partially solidi CH5 fies upon standing at room temperature. The crude prod uct is purified by recrystallization from an 80:20 ethanol: having a melting point of 70–70.5 C, the infrared spec water mixture. There is obtained 247 grams 55% yield) trum of which shows bands at 5.73p and 5.92u. Anal of a white crystalline product having a melting point of ysis, calculated for C15HFNOs: C, 27.8; H, 1.24; N, 53-54.5° C. consisting of N-ethyl-perfluoro(9-methyl 2.16; molecular weight, 649. Found: C, 27.8; H, 1.27; 30 N, 2.12; molecular weight (neutralization equivalent), decan) amide, 641. F. The potassium, sodium and ammonium salts of the CFCF (CF). CNHCH foregoing acid are prepared in the manner described in the infrared spectrum of which shows amide bands at Examples 3, 4 and 5 respectively. These salts are white 5.88w and 6.47. Analysis, calculated for CHFNO: crystalline solids. C, 26.4; H, 1.02; N, 2.37; F, 67.5. Found: C, 26.5; H, Example 19-Preparation of N-perfluoro(13-methyl 0.88; N, 2.46; F, 68.2. (b) Preparation of tetradecanoyl)aminoacetic acid 40 A solution of 9.74 grams (0.011 mole) of perfluoro(13 (r. 9 methyltetradecyl chlorosulfate CFCF (C F.CN-CHC OO CE Cas gr. About 1 gram (0.04 gram atom) of reagent grade Socium CF3 CFCFliOSOC is added to 250 milliliters of anhydrous toluene and the 45 in 50 milliliters of hot anhydrous dimethoxyethane is mixture heated at reflux until the sodium melts. To slowly added to a stirred suspension of 13.5 grams (0.18 this mixture there is added slowly with continuous stir mole) of glycine, NH2CHCOOH, in 100 milliliters of ring 23.6 grams (0.04 mole) of the amide anhydrous dimethoxyethane and the mixture is refluxed under dry nitrogen for 7% hours. The reaction mixture (F. 50 is filtered to remove 13.0 grams of insoluble material and CFCF (CF). CNHCH the solvent of the filtrate is removed by distillation in prepared as described above, and the mixture refluxed Vacuo at a pot temperature of 50 to 60° C. The residue for 8 hours under anhydrous conditions. A light brown is extracted with four 100 millimeter portions of petroleum solid is formed. The toluene which forms as a super ether (a hydrocarbon mixture boiling from 30 to 60° C.) natant liquid is pipetted out of the reaction flask under 55 a flow of nitrogen after which 200 milliliters of anhy followed by extraction with four 100 milliliter portions drous diethylene glycol dimethyl ether, is introduced. of diethyl ether. The diethyl ether extract is filtered, There is then added 13.4 grams (0.08 mole) of ethyl Washed with four 50 milliliter portions of water, dried bromoacetate, BrCHCOOCH5, and this mixture re With anhydrous magnesium sulfate and evaporated on a fluxed for 30 hours. The reaction mixture is filtered to 60 Steam bath to yield 3.5 grams (39% yield) of a white remove insoluble material after which the solvent of the Solid residue having a melting point of 161.5-163° C. filtrate is evaporated under reduced pressure. The Recrystallization of this product from a mixture of di liquid residue is distilled and there is obtained 12.6 grams methoxyethane and benzene in the ratio of 1:10 provides (45% yield) of an oily product having a boiling point a pure product having a melting point of 164.5-165.5° C. of about 130° C. at about 0.1 mm. Hg having the struc 65 consisting of the amido acid ture CF3 O (F 9 1. CF3 CFCF2CNECHCOOH CFCF (CF);CN-CH.C OO CH Analysis, calculated for CHFNOs: C, 24.9; H, 0.49; C2H5 70 N, 1.71. Found: C, 25.0; H, 0.68; N, 1.69. the infrared spectrum of which shows an ester band at The compounds prepared according to the foregoing ex 5.7 u and an amide band at 5.9. Analysis, calculated amples having a terminally branched perfluoroalkyl chain for CHFNO3: C, 30.1; H, 1.79; N, 2,07. Found: represent particularly preferred embodiments of the inven C, 30.3; H, 1.82; N, 2.14. tion. The following groups of compounds are of especial 8,238,285 14. 3 A necessary property of such self-polishing wax emul value both from the standpoint of ease of preparation and Sions is that they spread easily and evenly on all types of desirable properties: floor surfaces to produce a uniform, high gloss film upon drying without the necessity of buffing. A formulation (r. 9 having this property is said to have good "leveling' char CF3 CFCF). CNHCHCOOM 5 acteristics. In order to achieve good leveling charac teristics it is customary to employ a small amount of a so (r. 9 called "leveling agent” whose function is to reduce the CFCFCF, CNHCH2CH3COOM Surface tension of the emulsion and thus produce good Wetting of the surface to be coated. This wetting pro F. : 10 motes the leveling of the liquid film producing a uniform CF3 CFCF), UNCHCOOM coating of the film former covering the entire surface. H3 Because of their remarkable surface properties, com pounds containing a relatively long perfluorocarbon chain, where n is an integer from 5 to 10, and preferably from such as relatively long chain carboxylic acids and sulfonic 7 to 9, and where M is hydrogen, alkali metal or ammoni 5 acids and various derivatives thereof have been employed l The new compounds of the invention are characterized for this purpose. Because of the high cost of these ma by their extraordinarily high surface activity. As men terials, it is highly desirable that they be effective in the tioned previously they have been found to be more effec Smallest possible concentrations, and the minimum concen tive in a marked and Surprising degree than the perfluo 20 tration at which the fluorinated compound will produce rinated acids from which they are derived, as well as being Satisfactory leveling is a measure of its effectiveness. more effective than analogous derivatives of such acids. The following comparative tests in which various fluo They have likewise been found more effective than analo rinated compounds, including those of the invention, were gous compounds derived from perfluorinated sulfonic incorporated in a standard Self-polishing wax formula 25 tion illustrate the extraordinary surface properties of the acids.One particularly advantageous application for the com compounds of the invention. In these tests, a standard pounds of the invention is their use as leveling agents for formulation, designated Formulation A, having the fol aqueous wax and/or resin emulsions which are widely lowing composition, was employed: used in the form of so-called self-polishing wax formula 30 tions which dry to a shine without buffing. These formu FORMULATION A lations comprise basically an aqueous phase which gen Parts by erally comprises at least about 50% and usually from 50% Component: Weight to 90% by weight of the formulation and dispersed in Aqueous dispersion containing 30% by Weight the aqueous phase a non-volatile film forming material of polyethylene resin particles having melting which is usually a wax and/or a natural or synthetic resin point 213-221 F. ------222 which generally comprises from 10 to 50% by weight of Aqueous dispersion containing 15% by weight the formulation, and a minor amount e.g. from 1-10% of acrylic resin (Rhoplex B-83) -- 1150 by weight of an emulsifying agent which serves to keep Diethylene glycol monoethyl ether, the film formed dispersed in the aqueous phase. Minor CH2OHCH2OCHCHOCH 60 amounts of other modifying agents notably plasticizers Nonyl phenol-ethylene oxide condensation may also be included. product, 9-10 mois ethylene oxide/mol of Suitable film forming materials include natural and syn Peno ------. 12 thetic waxes such as carnauba, candellila, ouricury, bees Tri(2-ethylhexyl) phosphate ------14 wax, paraffin wax, microcrystalline waxes, montan and 45 Distilled water ------III 1968 the like. Suitable film forming resins include e.g. shellac, polyethylene, polystyrene, polyacrylates, such as poly To this formulation there was added Varying amounts butylacrylate, polyvinylacetate, polyvinylchloride, and of various fluorinated leveling agents, including the com various copolymers such as copolymers of vinylidene 50 pounds of the invention, and the minimum concentration chloride and acrylonitrile, and the like. at which effective leveling was observed was determined In some cases, a portion of the film former component in each case. In order to obtain strictly comparative may comprise an alkali soluble resin such as terpene modi data, the same test procedures and the same type of sur fied phenolic resins, or rosin maleates or rosin fumarates. face to be coated were employed in each case. The test Such resins, usually employed in minor amounts relative 55 procedure was as follows: to the other film formers, improve leveling characteristics A section of tile, 4%' x 4%' is laid horizontally with and also enhance the removability of the polish with the finished surface upward. A teaspoonful (approxi standard detergents. The film forming material may in mately 5 milliliters) of the polish formulation is poured clude mixtures of waxes, mixtures of resins, or mixtures onto the tile surface. Using only the bottom of the of waxes and resins. Suitable emulsifying agents serving 60 Spoon, the liquid is spread until the entire surface aca to keep the film former dispersed in the aqueous phase is covered. The tile is then set into a vertical position include e.g., anionic emulsifiers such as oleates or stearates to allow the excess liquid to drain and the coating to dry. of triethanolamine or of morpholine, alkali metal soaps A visual inspection of the surface was made after ap of fatty acids such as sodium stearate or sodium oleate; proximately ten minutes. The minimum effective CO cationic emulsifiers such as quaternary amine salts, e.g. 65 centration is that which produces a completely coated trimethyl octadecyl ammonium chloride, or fatty amine Surface with no puddling or heavily coated areas and acetates such as n-dodecyl amine acetate; nonionic emulsi Which dries to a uniform glossy film. The tile employed fying agents such as condensates of ethylene oxide with in these tests had a surface composed of unfilled poly alkylated phenols or condensates of ethylene oxide with 70 vinylchloride selected because of the difficulty of obtain fatty acids such as oleic or stearic acid. ing good leveling on such a surface. Suitable plasticizers, which are usually added in small in a first series of tests, a series of the compounds of amounts, include, for example, phosphate esters such as the invention having from 8 to 12 carbon atoms in the tricresyl phosphate, tributylmethyl phosphate, and phthal perfluoroalkyl portion CnF2n+1 were tested to determine ate esters such as dibutylphthalate and the like. 75 their minimum effective concentration, while at the same 3,238,235 5 6 time, corresponding perfluorocarboxylic acids having the seven carbon atoms in the perfluoroalkyl portion and same number of carbon atoms in the perfluoroalkyl por in the other fourteen carbon atoms. The results of these tion were similarly tested for minimum effective concen tests are shown in Table III. tration for producing satisfactory leveling. The results of these tests are shown in Table I. 5 Table III

Table I Leveling activity (minimum Leveling activity O Compound (as potassium salt) concentration (minimum percent by wt. in concentration Formulation A Compound (as NIH4 or alkali metal salt) percent by wt. in for satisfactory Formulation A leveling) for satisfactory leveling) ClF15CONEICH2CH2COOH------CsCONHCH2CH3COOH CsF1CONFICHCOOH---- CsF17COOH------0.20 CEF2CONHCHCOOH CFCONHCHCOOH--- 0.08 Csf7CONHCB2CH2COOH 0.08 C12FsCONHCH3COOH CsFCON(CH3)CHCOOH 0.08 C1F29CONHCHCOOH C10 F21COOH------0.0 CoFCONEICH2COOH------0.04 CoF1CONHCH2CH2COOH--- - 0.05 20 CoFCON(CH3)CEICOOH.-- - - 0.04 CoF2CONH(C2H5)(CH3COOH -- 0.04 C12.F2sCOOH------...-- - - 0.075 As is apparent from the data in Table III, the extraor CF25CONFICEICOOH------0,03 dinary leveling activity depends critically upon the C12F25CON(CH3)CHCOOH---...------0.03 number of carbon atoms in the perfluoroalkyl portion. 25 In the case of the compound having seven carbon atoms in the perfluoroalkyl portion, the minimum annount of As it is apparent from the above data, in each case, the leveling agent increased almost four-fold in contrast to required concentration in the wax formulation to produce the performance of the next compound in the series con satisfactory leveling for the compounds of the invention 30 taining eight carbon atoms in the perfluoroalkyl portion. was only half or less than half that required for corre Even more surprisingly, the same diminishing activity sponding perfluorinated carboxylic acids having the same is observed as the number of carbon atoms in the per number of carbon atoms. fluoroalkyl portion is increased to fourteen. Note that In a second series of tests, a series of compounds of the the minimum required effective concentration increases invention having eight carbon atoms in the perfluoroalkyl 3. more than twelve-fold as the number of carbon atoms portion CFan were tested for leveling activity against in the perfluoroalkyl portion increases from 12 to 14. analogous compounds having the same number of carbon The extraordinarily high surface activity of the com atoms in the perfluoroalkyl portion. One of these was pounds of the invention, as illustrated by the foregoing a sulfonamide derivative CaFSO2N(C2H5)CHCOOH data, is highly advantageous in that it permits the com while in another case an aminobenzoic acid derivative of 40 pounds to be employed in considerably lower concentra a perfluorinated carboxylic acid having eight carbon tions at a corresponding considerable savings in cost. The atoms in the perfluoroalkyl group was tested. The results required concentration of leveling agent will rarely exceed of these tests are shown in Table II below. about 0.1% by weight and will generally be used in con centrations of the order of 0.0001 to 0.05% by weight. The test formulation employed in the foregoing tests is Table II a difficult one to level on any surface and the polyvinyl chloride surface employed is one which is quite difficult Leveling activity (minimum to wet and further increases the difficulties in obtaining concentration good leveling. Since in most cases the leveling difficulties Compound (as NH or alkali metal salt) percent by wt. in 50 Formulation A will not be as severe, the compounds of the invention will for satisfactory usually be employed in considerably lower concentrations leveling) than those indicated in the foregoing tests. In the case CSFSO2N (C2H5)CH2COOH------0.12, for example of formulations such as the following used 5 5 Precipitates to coat substrates such as rubber tile, linoleum, vinyl as CgFCONE- -COOH------ineffective at all bestos tile and the like, the compounds of the invention concentrations. will be employed in concentrations of the order of CF7 CONHCH2COOH------0.08. 0.0001% to 0.02% to give satisfactory leveling character CFCONHCH2CH2COOH------0.08. CFCON (CH3)CH2COOH------0.08. istics: 60 EORMULATION B Parts by Component: weight As it is apparent from the data in the table above, the Aqueous dispersion containing 36% by weight perfluorinated carboxylic acid derivatives of the invention of polystyrene particles having an average in each case provided satisfactory leveling at a 50% 65 particle size of about 0.03 micron contain lower concentration than that required for the analogous ing emulsifying agent ------420 sulfonic acid derivative. The aminobenzoic acid deriva Shellac ------26.8 tive of the perfluorinated carboxylic acid was ineffective Ammonium hydroxide ------4 at all concentrations; precipitation occurred and essen Aqueous dispersion containing 30% by Weight tially no leveling effect was produced. 70 of polyethylene resin particles having melting In a third series of tests, a series of the compounds of points of 213-221 F. ------260 the invention containing from 8 to 12 carbon atoms in Terpene-phenolic alkali soluble resin ------14 the perfluoroalkyl portion CF2 were tested for level Distilled water ------920 ing activity against similar compounds having in one case 75 Tri(2-ethylhexyl)phosphate ------22 3,238,235 17 18 EORMULATION C (a) Preparation of monomer: A solution of 56.6 grams Parts by (0.1 mole) of Component: weight Aqueous dispersion containing 15% by weight (r. 9 CFCF (CFl; CF of acrylic resin (RhopieX B-83) ------725 5 Ammonium hydroxide solution of alkali soluble in 50 milliliters of anhydrous diethyl ether is added slowly phenolic resin containing 15% by weight of to a stirred solution of 46.3 grams (0.25 mole) of tertiary resin ------165 butylaminoethyl methacrylate, Aqueous dispersion containing 30% by weight O of polyethylene resin particles having melting points 213-221 F. ------110 IO (CH3)3CNHCH2CHO C--CH, CH3 CHOHCHOCHCHOCHsNonyl phenol-ethylene oxide - - - - condensation------1. 5 in 100 milliliters of anhydrous diethyl ether under dry product, 9-10 mols ethylene oxide/mol of nitrogen. During the addition, a small amount (0.5 phenol ------3 gram) of a very fine white precipitate is formed which is Tri(2-ethylhexyl)phosphate ------3.5 filtered off after refluxing the reaction mixture for 4.5 hours. The filtrate is washed with 200 milliliters of water FORMULATION ID followed by four 100 milliliter portions of 1 NHCl, then Component: Parts by with four 100 milliliter portions of 5% sodium bicarbon Part (a)- weight 20 ate solution and finally dried with anhydrous magnesium Carnauba wax------135 sulfate, and evaporated on a steam bath to yield 60.0 Microcrystalline wax ------67.5 grams (82% yield) of a liquid residue which solidifies Oleic acid ------24.8 slowly on standing at room temperature. This product, Caustic soda ------3.6 having a melting point of 42.5-43.5° C., has the structure Borax ------6.8 25 Distilled Water ------1125 (F Part (b)- Shellac ------37.7 CFCFC Flo-NCHCHO bi-oh, Ammonium hydroxide (concentrated) - 7.3 CH-i-CH, CH3 Distilled Water ------105 30 The infrared spectrum of this compound shows an ester Formulation D is made up by mixing 454 parts by band at 5.76 u, an amide band at 5.9p, and a 6.1a peak volume of Part (a) with 109 parts by volume of Part (b) characteristic of a double bond. Analysis, calculated for and 346 parts by volume of distilled water. C2HFNO3: C,34.6; H, 2.48; N, 1.92. Found: C, 34.5; H, 2.61; N, 1.72. FORMULATON E. (b) Homopolymerization: A solution of 5 grams of the Component: Parts by above monomer in 4.0 milliliters of acetone is placed in a Part (a)- weight 7 oz. glass bottle. To this solution is added about 0.2 Aqueous dispersion containing 36% by gram of the potassium salt of the compound of Example weight of polystyrene particles having 40 14, i.e. an average particle size of about 0.03 CF3 O micron ------8000 Dibutylmethyl phosphate ------192 CF,8 CFCFlsbricFil. -NCH.cook Dibutyl phthalate ------240 C3 Distilled Water ------16,864 45 dissolved in 11.0 milliliters of deoxygenated, deionized Part (b)- - water together with 0.15 gram of potassium persulfate as Aqueous dispersion containing 30% by polymerization catalyst. The bottle is filled with nitro weight of polyethylene resin particles gen, capped, placed in a bath held at a constant tempera having melting points of 213-221 F.- 110 ture of 50° C., and maintained at this temperature with Oleic acid ------22 agitation for a period of 41 hours. There is obtained Morpholine ------22 50 from this reaction a latex having a solids concentration of Distilled Water ------846 about 25% by weight and containing about 5 grams of Part (c)- - polymer having the repeating units Shellac ------450 Sodium tetraborate (borax) ------54. or F3 Distilled Water ------3696 5 5 g-f Formulation E is made up by mixing 60 parts by volume CF, of Part (a) with 10 parts by volume of Part (b) and 30 CH3 C=O parts by volume of Part (c). CEs-C-N In addition to their use as leveling agents in so-called 60 self-polishing wax formulations as described above, the Cha C2 compounds of the invention are also useful as surfactants CH in the emulsion polymerization of ethylenically unsatu rated compounds such as olefins, acrylates and the like, O particularly in the polymerization or co-polymerization of fluorinated olefins and acrylates. The following exam -- (-CH -- ples illustrate the use of the compounds of the invention for such applications. L &H, J. The homopolymer latex produced is ideally suited for the Example 20.-Homopolymerization of 70 treatment of textiles and other fibrous materials in order CF O O to render them resistant to Wetting by both aqueous and oleaginous systems. The textiles or other materials im C Fabric Fé-NCHCH-obc=CH, pregnated with such a latex are remarkably water and oil CE-C-CH3 &H, repellant due to the long chain perfluoroalkyl groups con H3 75 tained in the polymer chain. 3,238,235 20 (c) Copolymerization: The same procedures as de Example 23.-Polymerization of scribed above for the homopolymerization are followed except that to the polymerization recipe employed for (F. homopolymerization there is added 5.0 grams of butyl CFCCFC FC-NCHCHO CC-CH methacrylate as a comonomer and an additional 6 milli CEI-C-C-3 CE: liters of deoxygenated, deionized water. There is ob tained approximately 10 grams of a copolymer in the form CH3 of an aqueous latex having similar utility as the homo (a) Preparation of the monomer: To a stirred solution polymer. of 46.3 grams (0.25 mole) of tertiary butylaminoethyl Example 21.-Polymerization of methacrylate in 150 milliliters of anhydrous diethyl ether O there is added drop by drop 68.2 grams (0.1 mole) of the CF3 O O acid fluoride C Fé FC File-NCHCH-0 &c=CH, GF. Q CH-C-CF3 &H, CF2Cl CFCFCF bH, under nitrogen. The reaction is mildly exothermic and an insoluble material is formed during the addition period. (a) Preparation of monomer: Following the proce The mixture is refluxed for three hours and then filtered to dures of Example 20, the acid fluoride remove 1.5 grams of a white solid. The filtrate is washed with five 100 milliliter portions of 1 NHCl followed by (F 20 washing with three 100 milliliter portions of 5% sodium CFCF (CFls CF bicarbonate solution and then with 100 milliliters of water. is reacted with tertiary butylaminoethyl methacrylate to The organic layer is separated, dried with anhydrous mag provide a white crystalline product in 87% yield having nesium sulfate and evaporated on a steam bath to provide a melting point of 41.5-42 C. and having the structure 68.3 grams (81% yield) of a colorless liquid which solidi shown above. The infrared spectrum of this compound 25 fies slowly on standing at room temperature. This prod shows characteristic bands at 5.79 u, 5.9a and 6.1 u. An uct has a melting point of 56-57.5 C, and has the strcture alysis, calculated for C19H28FNOs: C, 36.1; H, 2.87; CF3 O O N, 2.22. Found: C, 36.2; H, 3.10; N, 2.37. (b) Polymerization and copolymerization: Following CF.C., FC F.). -NCHCH-0 C=CH the procedure of Example 20, and employing as the sur 30 CH3-C-CE ÖH, factant the potassium salt of the compound of Example ch, 2, i.e. Its infrared spectrum shows characteristic bands at 5.78u, CF3 O 5.9p, and 6.1 p. Analysis calculated for C28H18C1F24NO3: CF's CFC F&NHCH, ok 35 C, 32.6; H, 2.14; Cl, 4.18; N, 1.65. Found: C, 32.4; H, 2.27; Cl, 4.30; N, 1.64. the above monomer is homopolymerized to form a latex (b) Homopolymerization and copolymerization: Fol containing approximately 25% solids. Following proce lowing the procedures of Example 20, the above mono dures similar to those used in Example 20, and using the mer is homopolymerized in the presence of the potassium above surfactant, the above monomer is copolymerized 40 salt of the product of Example 11, i.e. with an equal weight of neoprene. CF3 Example 22-Polymerization of C F.C. FCFls CNHICEICH2COK CF3 O O to produce a latex of the homopolymer. The latex thus 45 produced is useful for the impregnation of textiles and C Fé FIC Flé-NCHCH.0 &c=CH, other fibrous materials to impart a high degree of water CH-)-CH, &H, repellancy and a moderate resistance to wetting and stain &H, ing by oleaginous systems. A copolymer of the above (a) Preparation of monomer: Following the procedure monomer with butyl methacrylate is produced following of Example 20, the acid fluoride 50 the procedures of Example 20 and using the above sur factant. This copolymer has similar utility for the im CF3 pregnation of textiles and other fibrous materials to im cFéFICF). F part water and oil repellancy. is reacted with tertiary butylaminoethyl methacrylate and there is obtained a white crystalline solid having the 55 Example 24-Polymerization of Structure F. CF3 O O CF2Cl CFC Fill-NCHCH.0 C=CH C Fé FC Flé-NCHCH-0 C=CH2 CH-)-CH, H3 CEI-C-CH3 ÖH, 60 &H, &H, (a) Preparation of the monomer: Following the pro (b) Homopolymerization and copolymerization: Fol cedures of Example 23, the acid fluoride lowing the procedures of Example 20, the above monomer CF3 O is homopolymerized in the presence of the ammonium Crcié FICF), F salt of the compound of Example 8, i.e. is reacted with tertiary butylaminoethyl methacrylate to provide an 80% yield of a white solid material having F. : the above structure and having a melting point of 34-35° CF3C Fiori.cnch.cooNH, C. The infrared spectrum of this product shows char CE8 acteristic bands of 5.8u, 5.9a, and 6.1a. Analysis, cal culated for C2H8ClF2NO3: C, 33.73; H, 2.43; Cl, 4.74; to provide a homopolymer in latex form. Using the same N, 1.87. Found: C, 33.67; H, 2.51; C1, 4.69; N, 1.85. surfactant, the same monomer is copolymerized with (b) Polymerization and copolymerization: Following about an equal weight of butadiene to provide the copoly the procedures of Example 20, the above monomer is mer in the form of an aqueous latex. 75 homopolymerized in an aqueous medium using a surfac 3,238,235 21 22 tant consisting of the ammonium salt of the product of 13; where R is an alkylenne group having from 1 to 3 Example 12, i.e., carbon atoms; and where M is selected from the group consisting of hydrogen, alkali metal and ammonium. CF3 O O 7. Compounds in accordance with claim 6 in which CFéFICF). (NHCHCHéoNH, 8)5 said perfluoroalkyl group contains from 10 to 12 carbon There is obtained an aqueous latex containing approxi atomS. mately 20% solids useful for imparting water and oil 8. Compounds of the formula repellancy to textile fabrics and the like. Following the procedures of Example 20 and using the same surfactant O O in an aqueous emulsion polymerization system, the above C. F-8-N-R-C-OM monomer is copolymerized with an approximately equal 0 k weight of butyl methacrylate to produce an equeous latex where CF-1 is a perfluoroalkyl group having from useful for similar applications. 8 to 13 carbon atoms and having a chain length of at In addition to their utility as leveling agents for self least 7 carbon atoms; where n is an integer from 8 to polishing aqueous wax emulsions and as surfactants in 5 13; where R is an alkyl group having from 1 to 2 carbon emulsion polymerizations, the compounds of the inven atoms; where R' is an alkylene group having from 1 to tion are also useful in the form of free acids as inter 3 carbon atoms; and where M is selected from the group mediates for the formation of Werner type chrome com consisting of hydrogen, alkali metal and ammonium. plexes which in turn are useful for the impregnation of 9. Compounds in accordance with claim 8 in which leather, paper and other fibrous materials to impart a 20 said perfluoroalkyl group contains from 10 to 12 carbon high degree of water and oil repellancy thereto. atoms. We claim: 10. Compounds of the formula 1. Compounds of the formula CF3 O O O 25 CFéFICF). 'NHCH.cooM C.F.-N-R-E-OM where m is an integer from 5 to 10 and where M is se R lected from the group consisting of hydrogen, alkali where CFan1 is a perfluoroalkyl group having from metal and ammonium. 8 to 13 carbon atoms and having a chain length of at 11. Compounds of the formula least seven carbon atoms; where n is an integer from 8 30 CF3 to 13; where R is selected from the group consisting of hydrogen and alkyl groups having from 1 to 4 carbon cFéFICF). NHCH-CHCOOM atoms; where R' is selected from the group consisting of where m is an integer from 5 to 10 and where M is se alkylene and monohydroxy alkylene radicals having from lected from the group consisting of hydrogen, alkali metal 1 to 6 carbon atoms; and where M is selected from the 35 ‘and ammonium. group consisting of hydrogen, alkali metal and am 12. Compounds of the formula: monium. CF3 2. Compounds in accordance with claim 1 in which cf. Fic F2C-N-CHCOOM said perfluoroalkyl group has from 10 to 12 carbon atoms. 40 E3 3. Compounds in accordance with claim 1 in which R where m is an integer from 5 to 10 and where M is se is hydrogen. lected from the group consisting of hydrogen, alkali 4. Compounds in accordance with claim 1 in which R metal and ammonium, R is an alkyl group having 1 to 2 carbon atoms. 5. Compounds in accordance with claim 1 in which 45 References Cited by the Examiner R’ is an alkylene group having from 1 to 3 carbon UNITED STATES PATENTS atOms. 2,764,602 9/1956 Ahlbrecht ---- 260-404.5 6. Compounds of the formula: 2,764,603 9/1956 Ahlbrecht ------260-404.5 O O 50 2,943,099 6/1960 Dohr et al. ------260-404.5 CF2C-NH-RCOM 3,091,623 5/1963 Knox et al. ------260-404.5 where CFani is a perfluoroalkyl group having from CHARLES B. PARKER, Primary Examiner. 8 to 13 carbon atoms and having a chain length of at least 7 carbon atoms; where n is an integer from 8 to JOSEPH. P. BRUST, Assistant Examiner.