United States Patent Office Patented Mar
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3,651,105 United States Patent Office Patented Mar. 21, 1972 3,651,105 CHROMUM COMPLEXES OF FILUOROISO ALKOXYALKYL CARBOXYLCACDS Louis G. Anello, Basking Ridge, Edward Michael Boghosian, Fort Lee, Edward S. Jones, Whippany, Pritam S. Minhas, Morris Plains, Alison K. Price, Mor ristown, and Richard F. Sweeney, Randolph Township, Dover, N.J., assignors to Allied Chemical Corporation, New York, N.Y. No Drawing. Filed Nov. 1, 1968, Ser. No. 772,849 0 nt. C. C08h 17/36 wherein R1 and Ra have the meanings given above, with U.S. C. 260-414 7 Claims telomerizable unsaturated compounds having the formula ZZCFCZ3Z4 and/or XXCFCXX, wherein Z-X and ABSTRACT OF THE DISCLOSURE X.1-X have the meanings given above. Suitable telom 5 erizable compounds include ethylene, tetrafluoroethyl Chromium complexes of fluorocarbon carboxylic acids ene, difluoroethylene, chlorodifluoroethylene, and the characterized by having a polyfluoroisoalkoxyalkyl tail like. The telomerization reaction can be initiated by heat wherein an ether oxygen atom links a fluorinated carbon or by a free radical initiator. atom connected to two fluoroalkyl groups and at least The polyhaloisoalkoxyalkyl iodides can be prepared one -CFCF-group. These chromium complexes are 20 by reacting a suitable halogenated ketone with an ioniz useful to impart oil and water resistance to various sub able fluoride salt, e.g. CsP or KF, to form a fluorinated strates, including paper, leather, and the like. organic salt, and reacting the organic salt with tetrafluoro ethylene and iodine. Preparation of the polyhaloiso alkoxyalkyl iodides is described in detail in copending This invention relates to novel chromium complexes 25 U.S. applications of Litt et al., Ser. Nos. 492,276 filed of fluorocarbon carboxylic acids which are useful for Oct. 1, 1965, now U.S. Pat. No. 3,453,333 and 513,574 treating a wide variety of substrates to impart oil and filed Dec. 13, 1965, now U.S. Pat. No. 3,470,256. The water resistance thereto. More particularly, this inven pertinent subject matter of these copending applications tion relates to chromium complexes of fluorocarbon car is hereby incorporated by reference. boxylic acids having a polyfluoroisoalkoxyalkyl tail, 30 The following series of equations will serve to further wherein an ether oxygen atom links a fluorinated carbon illustrate the preparation of the iodides, wherein R, R2, atom attached to two fluoroalkyl groups and a Z-Z, X-Xa, m and n have the meanings given above. -CF-CFrgroup The fluorocarbon carboxylic acids used in making the 35 chromium complexes of the invention have the formula: (1) R. Yc-F 40 in? Zi Z3 X XV X. R -o-crer ()2, 2./ (c.k, k, ) k. soon C-F R? 45 wherein R and R independently can be fluorine, chlorine, perfluoroalkyl or together can form a cyclic perfluoro alkylene group with the proviso that both R1 and R2 are 50 not chlorine; Z, Z2, Z, and Z are independently selected from the group consisting of hydrogen, fluorine and chlorine, providing the sum of Z-Z4 contains no more than 2 chlorine atoms; X1, X2, X3 and X4 are inde pendently selected from the group consisting of hydro 55 gen, fluorine and chlorine providing that no more than one of X-X is chlorine, and Xa cannot be hydrogen when X is halogen; and m and n are integers of 0-75 and the sum of m and n is from 0-75. Preferably, m and floor -- m21 ZaC=CZ3Z4 -> in are integers from 0 to 10. 60 The criticality in the structure of the above-described acids is in the polyfluoroalkoxyalkyl tail portion of the l, molecule wherein an ether oxygen atom links a fluori nated carbon atom attached to two fluoroalkyl groups and a -CFCF-group. 65 The above-described acids can be prepared from their corresponding polyhaloisoalkoxyalkyl iodides. The io R Z1 23 dides. The iodides and their preparation are disclosed in detail in copending U.S. application Ser. No. 633,359, R1 -o-oper();2. 2, filed Apr. 25, 1967, now U.S. Pat. No. 3,514,487. These 70 telomers are prepared by reacting polyhaloisoalkoxyalkyl Ye-F iodides of the formula: Ry 3,651,105 4 fluoride at a temperature between about 50-175 C., 4. preferably about 100-150° C. At least one mol of sulfur R trioxide is employed per mol of telomer iodide; pref erably an excess of about 2:1 to about 10:1 is employed. R –F Z Zg frequired to maintain the reactants in liquid phase, super atmospheric pressure is employed, suitably 25-500 p.s.i.g. F-C-O-CFCF ) -- axXC-CXX --> Higher molecular weight telomer iodides in general re Z/ in quire longer reaction time and higher reaction tempera tures for complete conversion. The product is generally O a mixture of the acid fluoride, pyrosulfuryl fluoride, un reacted starting material and small amounts of the free R acid. The products can be recovered from the mixture Yo-F by fractional distillation. The acid fluoride and pyrosul fury fluoride can be hydrolyzed to the desired free acid 15 by refluxing with water. Alternatively, the corresponding acid salts can be made by reaction with sodium or potas sium hydroxide and acidification with an aqueous mineral acid. The preparation of the acid starting materials is de 20 scribed in greater detail in copending U.S. application of It will be understood that when n and/or n is 0, the Anello et al., Ser. No. 721,117 filed Apr. 12, 1968. Other applicable telomerization Equations 3 and/or 4 are methods of preparing the fluorocarbon acids will be known omitted. to one skilled in the art. The fluorocarbon carboxylic acids described above can According to the preferred embodiment of the inven be prepared from the telomer iodides according to several 25 tion, chromium complexes of acids having the formula routes. Referring to the general Formula 1 the fluorocarbon carboxylic acids wherein n is at least 1 and wherein Xa Yo-F and X are both hydrogen can be prepared by reacting the appropriate iodide with SO3 to form the correspond X ing pyrosulfate, or with oleum to form the corresponding 30 F-C-O-CFCF (CFC F)-(CHOH).-C OO hydrosulfate. The pyrosulfate or hydrosulfate can be hy drolyzed with aqueous acid to form the alcohol. The alcohol can be oxidized with well-known oxidizing agents / such as potassium dichromate, potassium permanganate R or concentrated nitric acid to form the free acid. The 35 wherein R1 and R are fluorine or perfluoroalkyl of 1-2 preparation of the alcohols is described in greater detail carbon atoms, and n and n are integers from 0-10; X1 in a copending U.S. application of Anello et al., U.S. and X are hydrogen when n is 1 or more; and X and Xa Ser. No. 721,089 filed Apr. 12, 1968, now abandoned. are fluorine when n is 0, are particularly effective as The pertinent subject matter of that application is here sizing compounds for paper and as leather treating agents. by incorporated by reference. 40 The chromium complexes of the fluorocarbon car Fluorocarbon carboxylic acids of the general Formula boxylic acids described above are Werner-type coordina 1 wherein n=0 and X and X are hydrogen, fluorine or tion complexes. They are prepared in known manner by chlorine providing only one of X and Xa are either reacting a suitable acid as hereinbefore described with chlorine or hydrogen, can be prepared by oxidizing the chromyl chloride in an anhydrous solvent in the pres alcohol derived from telomer iodides as in Equation 4 ence of a reducing agent. wherein n=1 and X and X are both hydrogen. Other methods of preparing the chromium complexes Fluorocarbon carboxylic acids of the general Formula will be known to one skilled in the art. 1 wherein n=0 and X and X are both hydrogen, and The molar ratio of the acid to chromyl chloride is not the carbon atom in the B-position with respect to the critical and can vary over a wide range, but generally carboxyl group is substituted with two fluorine atoms, 50 from about 2 to about 20 mols of chromyl chloride per can be prepared by oxidation of a fluoroolefin containing mol of acid is employed. a terminal ethylene group having the formula: The reducing agents preferred are alcohols, which can also be used as the solvent for the reaction. Suitable alcohols include aliphatic alcohols such as methanol, Yo-F 55 ethanol, propanol, isopropanol, butanol, isopentanol, and the like. Excellent results are obtained with isopropanol. f Z F In addition to an alcohol solvent, other inert, anhydrous solvents can be employed including haloalkanes such as RF- -o-crer () clerc, chloroform, carbon tetrachloride, sym-dichloroethane and - 60 the like. The presence of an inert solvent is advantageous in avoiding excessive reaction temperatures since the re R? action between the acid and chromyl chloride is exo wherein R, R Z, Z and m have the meanings given thermic. In a preferred mode of operation, the chromyl above. These fluoroolefins can be prepared by reacting chloride is dissolved in an inert solvent such as carbon the corresponding telomer iodides with allyl alcohol at 65 tetrachloride and this solution is added slowly to the a temperature between about 100' to 450° C., pref acid solution, maintaining the temperature at or below erably between about 150 to 300° C., under super the reflux temperature of the reaction mixture. atmospheric pressure. The terminal ethylene group can The resultant green solution contains the chromium be oxidized by treating with potassium permanganate or complex of the acid.