Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
  • C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
  • C07C53/19—Acids containing three or more carbon atoms
  • C07C53/21—Acids containing three or more carbon atoms containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
  • C07C53/38—Acyl halides
  • C07C53/46—Acyl halides containing halogen outside the carbonyl halide group
  • C07C53/50—Acyl halides containing halogen outside the carbonyl halide group of acids containing three or more carbon atoms
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• This invention relates to terminally perfluoroalkylated aliphatic carboxylic acids and to derivatives thereof.
• Perfluoroaliphatic carboxylic acids and acids of similar type in which there is interposition of a methylene group between the carboxyl and perfiuoroalkyl groups are known.
• the latter may conveniently be designated as 2,2-dihydroperfiuoroalkyl carboxylic acids.
• These known compounds are strong acids containing over 50% combined fluorine in which the strength of the ordinary carboxyl group is enhanced by the proximity of the highly fluorinated alkyl groups. Fluorinated acids and derivatives thereof have desirable oleophobic and hydrophobic properties; but the strongly acid nature of the known compounds introduces certain disadvantages.
• the perfiuoro carboxylic acids approach the acidity of mineral acids and are highly corrosive and dangerous to handle. Their derivatives are relatively easily hydrolyzed and the metallic salt complexes of these strong acids tend to be labile.
• the 2,2-dihydroperfluoro-carboxylic acids are unstable in alkaline media.
• R is a monovalent, functionally unsubstituted perfluorinated group having from 4 to 12 carbon atoms and includes perfluorinated alkyl and cycloalkyl radicals, and R is a straightchain alkylene group having from 1 to 12 carbon atoms, have low acid strength while unexpectedly retaining the desirable oleophobic properties of the perfluorinated group.
• acids coming within the scope of the present invention there may be mentioned: 5-perfluorobutylpentanoic acid, 7-perfiuoroamylheptanoic acid, 6-perfluorododecylhexanoic acid, omega-perfluorobutyl-myristic acid, 9-perfluorooctyl-nonanoic acid, 5- perfluorooctylpentanoic acid, ll-perfluorooctyl-hendecanoic acid, l2-perfluorooctyl-dodecanoic acid, and 8- perfluorocyclohexyl octanoic acid.
• the acids of the invention and their derivatives retain the desirable oleophobic properties conferred by the R group and, when the alkylene group R is in the range of l to 12 carbon atoms, the soluble salts of these acids have a balance of fiuophilic, oleophobic and hydrophilic properties possessing particular value as emulsifying agents for use in the polymerization of monomers of the fluorocarbon type.
• fiuophilic is here coined to describe the novel property of afiinity for fluorocarbon-type materials, and includes both solubility and wettability phenomena involving such materials.
• the vinyl and allyl esters of the chlorinated precursor intermediates of the acids of the present invention of the type R -CH CHCl(CH CH CO H wherein n is 0 to 11, as well as the vinyl and allyl esters of the acids of the invention themselves, can be emulsionpolymerized in the presence of salts of these latter acids as emulsifying agents.
• carboxyllinked derivatives This term as used herein signifies derivatives formed both by replacement of the hydrogen ion of the carboxyl group by another cation, as in the salts and complexes, and derivatives formed by formal dehydration reactions as for example acyl halides, anhydrides, amides, amidines, nitriles, hydrazides, peroxides, esters, orthoesters and the like.
• the acids of the invention can be produced by successively dehydrohalogenating penultimately chlorinated acids formed, for example, by desulfonylative addition of a perfluorinated sulfonyl chloride to a terminally unsaturated aliphatic carboxylic acid and reducing the resultant fiuorinated unsaturated acids, for example, by hydrogenation.
• Intermediate terminally'unsaturated acids having the desired carbon chain lengths for preparation of the compounds of the invention can be prepared by hydrolysis of the alkenylmalonic esters produced by the repeated use of the malonic ester synthesis, described in the textbook of R. B. Wagner and H. D. Zook, entitled Synthetic Organic Chemistry, pages 427-428, John Wiley and Sons, Inc., New York, 1953.
• the compounds of the invention areconveniently and directly prepared by catalytic protodechlorination (reductive dehydrohalogenation) of the halogenated acids produced as set forth above.
• Still another method by which the acids of this invention can be produced is by addition of a perfluoroalkyl iodide to an unsaturated aliphatic acid, followed by catalytic protodeiodination, as illustrated by the equation:
• perfiuorinated acids of the invention are seen to possess in part the characteristics of organic carboxylic acids and in part those of perfluorinated acids. They are, generally speaking, low-melting somewhat waxy white or slightly colored solids which are substantially insoluble in water and hydrocarbon solvents, and are soluble in fluorocarbon solvents.
• these salts are readily soluble in water as, for example, the sodium, potassium and ammonium salts; or insoluble, as for example, the basic aluminum
• the basic aluminum salt is oleophobic and hydro phobic, but is unexpectedly found to be highly fluophilic, being soluble in fluorocarbon solvents.
• the acids of the invention can be converted to the corresponding acyl halides, for example to the acyl chloride, by treatment with conventional halogenating agents, such as phosphorus pentachloride and thionyl chloride; and to the acyl fluoride, by treatment of the acyl chloride with hydrogen fluoride; and the like.
• conventional halogenating agents such as phosphorus pentachloride and thionyl chloride
• acyl fluoride by treatment of the acyl chloride with hydrogen fluoride; and the like.
• the acyl chlorides can be converted to the corresponding acyl bromides or acyl iodides.
• the acids themselves, or especially their anhydrides or their acyl halides, can bereacted with alcohols to produce esters,
• the carboxyl group of the acids of the invention is capable of undergoing all of the ordinary reactions of the aliphatic carboxyl group.
• the esters can 'also be produced by transesterification of the acids with suitable esters such as vinyl acetate, this method being particularly useful for preparation of esters for which the free alcohol is not stable; or by catalytic esterification, particularly under conditions such that water is eliminated from the reaction mixture.
• suitable esters such as vinyl acetate
• catalytic esterification particularly under conditions such that water is eliminated from the reaction mixture.
• Other conventional reactions of carboxylic acids are also exhibited by 4 in the copending application of Olson et al., Serial No. 640,569, filed February 18, 1957.
• the vinyl and allyl esters of the acids of the invention can be homopolymerized and copolyrnerized inter se as well as with other monomers and low polymers to form polymeric materials comprising recurring units having the formula CHrCHz wherein R and R, have the significance set forth hereinabove and n is 0 or 1. These homopolymers and co polymers are suitable for rendering paper and textiles oil-resistant and water repellent.
• the 4-chloro-5-(perfiuorooctyl)-pentanoic acid thus prepared is hydrogenated by shaking a solution of 8.00 g. (0.0145 mole) of the acid and 2.5 g. (0.062 mole) of sodium hydroxide in a mixture of 30 ml. of water and 30 ml. ethanol for 3 hours at 140C. in a rocking highpressure hydrogenation apparatus, in the presence of 4 g. of Raney nickel catalyst and with hydrogen supplied at 2500 p.s.i. pressure. After removal of the catalyst and evaporation to dryness, an amorphous residue is obtained comprising sodium S-(perfiuorooctyl)-pentanoate.
• Example II An' electrically heated rocking autoclave of 187 ml.
• Example III A mixture of 54 g. (.0895 mole) of ll-(perfluorooctyl)-hendecanoic acid and 35 g. (0.28 mole) of thionyl chloride is warmed under reflux on a steam bath for about 1 hour, allowed to stand overnight at room temperature, and then heated to the point of vigorous refluxing for 2 hours. The resulting reaction mixture is transferred to a distilling flask and excess thionyl chloride is removed by distillation. Traces of thionyl chloride still remaining are removed by heating under reduced pressure and the residual 11-(perfluorooctyl)-hendecanoyl chloride is fractionally distilled under reduced pressure, the fraction boiling from 110 to 125 C.
• Example IV Omega-perfluorooctylhendecanoic acid is converted to a chromium complex by the method described in US. Patent 2,662,835 for fully fluorinated acids.
• the resulting green solid complex material cannot be structurally characterized by analysis. It is applied to chrome-tanned, split and shaved cowhide sides previously lightly retanned with vegetable extract in a wet handling drum and conventionally dyed.
• the chromium complex is applied as follows: The leather handling drum is drained, and
• fresh float water is introduced at 100 F. in amount approximately .equal to the weight of the wet leather, the
• Example VI Another route for the preparation of the acids of the present invention is exemplified by the following procedure:
• omegaperfluoroootyl-hendecyl bromide prepared by the reduction of omega-perfluorooctyl-hendecanoic acid with lithiurn aluminum hydride to the corresponding alcohol followed by treatment with hydrogen bromide
• a solution of 5.0 grams (.00765 mole) of omegaperfluoroootyl-hendecyl bromide prepared by the reduction of omega-perfluorooctyl-hendecanoic acid with lithiurn aluminum hydride to the corresponding alcohol followed by treatment with hydrogen bromide
• absolute ethanol is mixed with 2 ml. of an aqueous sodium cyanide solution containing 0.008 mole sodium cyanide and refluxed for 72 hours.
• the nitrile of omegaperfiuorooctyldodecanoic acid is thus formed.
• the omega-perfluorododecanonitrile can be isolated, as by removal of the solvent by evaporation followed by waterwashing to dissolve the soluble constituents of the reaction mixture and drying of the Water-insoluble residue, followed by recrystallization from cold ether, chloroform or alcohol.
• the omega-perfluorooctyl dodecanonitrile can be hydrolyzed to form the corresponding w-perfluorooctyl dodecanoic acid by addition to the alcoholic reaction mixture of 2.24 grams (0.04 mole) of potassium hydroxide dissolved in about 4 ml. of water and refluxing for 24 hours.
• Example VII To a mixture of 65 grams (0.75 mole) of vinyl acetate, 75 grams (0.125 mole) of 1l-perfluoroocty1-l0- hendecenoic acid (prepared by refluxing omega-perfluorooctyl-10-chlorohendecanoic acid for 2 hours with excess alcoholic potassium hydroxide and isolating and distilling the resultant acid) and 1.5 grams of mercuric acetate is continuously added 0.36 gram of concentrated sulfuric acid. The reaction mixture is allowed to stand at room temperature for about thirteen days to effect ester interchange.
• 1l-perfluoroocty1-l0- hendecenoic acid prepared by refluxing omega-perfluorooctyl-10-chlorohendecanoic acid for 2 hours with excess alcoholic potassium hydroxide and isolating and distilling the resultant acid
• 1.5 grams of mercuric acetate is continuously added 0.36 gram of concentrated sulfuric acid. The reaction mixture is allowed to stand at room
• Example VIII By employing substantially the same procedure as that 'set forth in Example VII, the vinyl ester of II-(perfluorooctyl)-hendecanoic acid is prepared. In this case, because of the lower solubility of the saturated acid, it is necessary to heat the mixture of 9 grams of acid, 7.75 grams of vinyl acetate and 0.18 gram of mercuric acetate to 40 C. until the acid does not precipitate from the mixture on cooling to room temperature. The mixture is then allowed to stand at room temperature for five days and worked up. The fraction boiling at about 125 to 132 C. at 0.35 mm. of mercury pressure is collected.
• the vinyl ester of 11perfluorooctyl-hendecanoic acid thus prepared is a soft solid which melts at about 38 C. Analysis-Found, 40.4% C, 51.2% F; calculated, 40.1% C, 51.3% F.
• the amount of mercuric acetate employed in the procedure can be varied slightly with substantially the same results.
• Example IX Vinyl 1l-perfluorooctyl-10-ch1oro-hendecanoate, prepared by esterification of 1l-perfluorooctyl-10-chlorohendecanoic acid with vinyl acetate under conditions of ester interchange as hereinbefore disclosed, can be polymerized either in bulk or in emulsion form.
• a mixture of 1.0 gram of vinyl 11-perfiuorooetyl-10-chlorohendecanoate and 0.01 g. of 25% solution of acetyl peroxide in dimethyl phthalate is heated under vacuum in a sealed ampoule at 50 C. for 42 hours.
• a rather hard, opaque, waxy polymer is formed which is insoluble in acetone. It is dissolved in xylene hexafluoride and precipitated with methanol, collected and dried in vacuurn at 50 C.
• Emulsion polymerization of vinyl ll-perfiuorooctyl- 10 chloro-hendecanoate is effected using 1.0 g. monomer, 1.8 g. water, 0.05 g. of the potassium salt of 11- (perfluorooctyl)10-hendecanoic acid and 0.0030 g. potassium persulfate in an ampoule which is frozen, evacuated and thawed for two cycles before heating at 50 C. for 42 hours.
• the resulting latex contains 10% polymer solids, with inherent viscosity in 2:1 methyl perfluorobutyrate-acetone of about 0.32.
• Example X Vinyl 11perfluorooctyl-hendecanoate is emulsion homopolymerized by heating a mixture of 0.25 gram of the monomer, 0.46 g. of 2.8% aqueous dodecylamine hydrochloride solution and 0.0013 g. potassium persulfate. The resulting latex contains 14.8% solids, indicating 38% conversion. The intrinsic visocity in 2:1 methyl perfiuoro-butyrate-acetone is 0.32.
• R represents a monovalent, functionally-unsub-
• a copolymer is prepared from 20 g. of the above vinyl 11perfluorooctyl-hendecanoate and 1.47 g. of maleic anhydride (2:1 molar ratio) made up as 50% solution in toluene, to which 1% benzoyl peroxide is added. The mixture is refluxed 14 hours, a further 1% of benzoyl peroxide is added and after heating for 7 hours longer the solution is diluted to 35% solids with methyl ethyl ketone and precipitated with methanol, giving a polymer softening above 60 C. When applied to paper or cloth as a 5% solution in methyl ethyl ketone, and the solvent permitted to evaporate, the paper or cloth is rendered oil and water-repellent.
• esters are prepared by azeotropic removal of water with benzene or toluene from a mixture of the terminally perfluoroalkyl aliphatic acid and allyl alcohol using a sulfonic acid catalyst for the esterification.
• Esters are thus prepared from 6.0 g. (0.01 mole) of 11- perfluorooctyl-hendecanoic acid with 5.8 g. (0.10 mole) of allyl alcohol and from 16 g. (0.025 mole) of 11-perfiuorooctyl-10-ch1oro-hendecanoic acid with 10 g.
• esters are purified by distillation under reduced pressure.
• Example XII Following the procedure of Example I above, a mixture of 28.8 g. of perfluoro-(4-ethylcyclol1exane)sulfonyl chloride, 9.2 g. of IO-hendecenoic acid and 1.0 g. of di t-butyl peroxide is heated to 145 C. under reflux and held at that temperature for two hours. The reaction product is subjected to high vacuum distillation in a short path distilling apparatus. The fraction boiling at C. at 0.01-0.04 mm. is collected. A pasty brown solid is recovered, and is redistilled at 130 C. and 0.010 mm., to produce a mushy semi-solid comprising 10-chloro-ll-perfiuorm(4-ethylcyclohexyl)hendecanoic acid.
• a solution of 14.0 g. (0.023 mole) of the chlorinated acid of melting point 4648 C. and 4.0 g.(0.1 mole) of sodium hydroxide in a mixture of 40 rnl. each of ethanol and water is hydrogenated under 2500 psi pressure of hydrogen with Raney nickel catalyst for 3 hours at C., followed by 3 hours at 180 C. in a rocking autoclave as in previous examples.
• the workup furnishes an ambercolored oily acid which is recrystallized from methylene chloride at 25 C. to give the desired ll-(perfluoro-4- ethylcyclohexyl)hendecanoic acid melting at 55-60 C. Analysis.-Found, 41.4% C, 48.6% F; calculated, 40.3% C, 50.8% F.
• a compound of the group consisting of terminally perfluoroalkyl-substituted aliphatic carboxylic acids represented by the formula:
• stituted perfluorinated group having from 4 to 12 carbon atoms and R is a straight chain alkylene group having from 1 to 12 carbon atoms, and the carboxyl-linked derivatives thereof selected from the class consisting of cationic salts, cationic complexes, acyl halides, anhydrides, amides, amidines, nitriles, hydrazides, peroxides, esters and orthoesters.
• R represents a monovalent, functionally-unsubstituted perfluorinated group having 4 to 12 carbon atoms
• R is a straight chain alkylene group having 1 to 12 carbon atoms
• n is a number of the group consisting of 0 and 1.
• a process for the production of terminally perfluoroalkylated aliphatic carboxylic acids which comprises subjecting a halogenated acid represented by the formula:
• R represents a monovalent, functionally unsubstituted perfluorinated group having from 4 to 12 carbon atoms and RX represents a straight-chain alkylene group having from 1 to 12 carbon atoms and having a halogen other than fluorine attached to the carbon atom thereof which is adjacent to the methylene group connected to the said perfluorinated group, to the action of hydrogen under pressure in the presence of a hydrogenation catalyst.
• RX represents a monovalent, functionally unsubstituted perfluorinated group having from 4 to 12 carbon atoms and RX represents a straight-chain alkylene group having from 1 to 12 carbon atoms and having a halogen other than fluorine attached to the carbon atom thereof which is adjacent to the methylene group connected to the said perfluorinated group, to the action of hydrogen under pressure in the presence of a hydrogenation catalyst.
• R represents a monovalent functionally-unsubstituted perfluorinated group having 4 to 12 carbon atoms
• R is a straight chain alkylene group having 1 to 12 carbon atoms
• n is a number of the group consisting of 0 and l.
• R represents a monovalent, functionally-unsubstituted perfluororinated radical having from 4 to 12 carbon atoms and R is a straight chain alkylene group having from 1 to 12 carbon atoms.

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Cited By (15)

Citations (4)

• 1957
  • 1957-06-26 US US668027A patent/US2951051A/en not_active Expired - Lifetime
• 1958
  • 1958-06-25 DE DE19581419498 patent/DE1419498A1/de active Pending

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