US3311566A - Halogenated carboxylic acids - Google Patents

Halogenated carboxylic acids Download PDF

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US3311566A
US3311566A US495720A US49572065A US3311566A US 3311566 A US3311566 A US 3311566A US 495720 A US495720 A US 495720A US 49572065 A US49572065 A US 49572065A US 3311566 A US3311566 A US 3311566A
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acid
grams
mixtures
acids
mixture
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US495720A
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Hauptschein Murray
Miville Maurice
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Pennwalt Corp
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Pennsalt Chemical Corp
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Priority to GB1051175D priority Critical patent/GB1051175A/en
Priority to FR975857A priority patent/FR1402173A/fr
Priority to DE19641519546 priority patent/DE1519546B2/de
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Priority to US495720A priority patent/US3311566A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C305/00—Esters of sulfuric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/093—Preparation of carboxylic acids or their salts, halides or anhydrides by hydrolysis of —CX3 groups, X being halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/004—Surface-active compounds containing F

Definitions

  • This invention relates to synergistic mixtures of highly fluorinated monocarboxylic acids and water soluble deriv-atives thereof.
  • acids of intermediate length in particular perfluorooctanoic acid, are used commercially as high performance surfactants such as in the emulsion polymerization of fluorinated olefins such as tetrafluoroethylene, chlorotrifluoroethylene and the like.
  • the synergistic mixtures of the invention are comprised of perfluoro or monochloroperfiuorocarboxylic acids or derivatives thereof, of sufficient water solubility for surfactant activity, which compounds have the general formula ZCJnii-OX Where Z is selected from the'class consisting of fluorine and chlorine; where n is an integer from six to thirteen; Where the fluoroalkyl group ZC F has a chain length of from five to twelve carbon atoms, and where X is hydrogen or a cation.
  • the mixtures of the invention contain from 55% to 90% by weight of at least one compound of the above formula having a fluoroalkyl chain length of from five to seven carbon atoms and where n is not more than 8, and not more than 45% nor less than 10% by weight of at least one compound of the above formula having a fluoroalkyl chain length of from nine to twelve carbon atoms and where n is not more than 13.
  • fluoroalkyl chain length is meant the longest straight fluoroalkyl carbon chain in the compound ignoring branching.
  • the mixtures contain from 60% to of at least one compound of the above formula having a fluoroalkyl chain length of from five to seven carbon atoms and from 20% to 40% of at least one compound having a fluoroalkyl chain length of from nine to twelve carbon atoms. Best results are obtained when the mixture comprises at least three compounds with at least two of the compounds having a fluoroalkyl chain of from five to seven carbon atoms in length and having not more than 8 carbons in the fluoroalkyl group and,
  • mixtures of the above type wherein the compounds are the free acids or the alkali metal, ammonium, or'alkyl substituted ammonium salts thereof; in other words, where X is selected from the class consisting of hydrogen, alkali metal (particularly sodium and potassium), ammonium or alkyl substituted ammonium, such as methylammonium, ethylammonium, dimethylammonium, diethylammonium, trimethylammonium, etc.
  • the mixtures of the above acids or water soluble derivatives thereof may be prepared in a number of ways.
  • a preferred method is to start with perfluorinated or monochloroperfluorinated iodides of the proper chain length.
  • These fiuorinated iodide precursors may be prepared by telomerization procedures such as by the reaction of 2-io-doperfluoropropane, CF CFICF or 2-iodoperfluoroethane CFgCFzI, with tetrafluoroethylene to produce telomers of the formula (CF CF[CF CF ],,I and CF CF [CF CF ],,I respectively; or by the reaction of l-chloro 2 iodo hexafluoropropane, CF CFICF CI or 1-chloro-2-iodotetrafiuoroethane CF ClCF I with tetrafluoroethylene to produce telomers of the formula.
  • telomer iodides Suitable procedures for preparing the precursor telomer iodides are described for examples in U.S. Patent 3,156,732 of Murray Hauptschein et al.
  • the precursor perfluorinated or monochloroperfluorinated iodides may be converted to the acid by reaction of the iodide with chlorosulfonic or fluosulfonic acid following the procedure described in detail in co-pending application Ser. No. 310,500, filed Sept. 20, 1963 of Murray Hauptschein and Milton Braid for Halogenated Organic Compounds.
  • the perfluorin-ated or monochloroperfluorinated chlorosulfates or fluosulfates thus obtained may be readily hydrolyzed to the acid.
  • the precusor perfluorinated or monochloroperfluorinated iodides may likewise be converted to the acids by the reaction of the iodides with fuming sulfuric acid as described in co-pending application Ser. No. 212,137 filed July 24, 1962 of Murray Hauptschein et al. Such a reaction produces a mixture of acid and acid fluoride.
  • the acid fluoride may be readily hydrolyzed to the acid by known procedures.
  • the desired mixtures of acids or derivatives in the proper proportions may, if desired, be obtained by starting with a mixture of iodides which will give the desired mixture of acids in the final product. Since the -CF I group of the iodides is converted to the carboxyl group in the process, the starting iodide should, of course, have one more carbon atom in the fluoroalkyl portion than is desired in the fluoroalkyl portion of the final product.
  • the lower members having up to about eight carbon atoms in the entire molecule may be prepared if desired by the electrochemical fluorination of the corresponding hydrocarbon carboxylic acid in liquid hydrogen fluoride as described for example in United States Patent 2,519,983 of Simons.
  • EXAMPLE 1 PREPARATION OF MIXED SUR- FACTANTS CFs CF2C1CF(CF2)11COOH This example illustrates the preparation of a mixture of acids and corresponding salts of the series CFzClCFKJFzMCOOH from the corresponding chlorosulfates.
  • a mixture of chlorosulfates consisting of about 28% by weight of R CF2ClCF(CF2CF2)2OSO2Cl 36% by weight of I CF2ClCF(CF2CF2)aOSOzCl 24% by weight of I CFzOlCF(OFgCF2)4OSOrOl and 12% by weight of is prepared from a mixture of the corresponding iodides consisting of i CF2ClCF(GFzOF2)2I B.P. 70 C. at 20 mm. Hg,
  • a 200 gram portion of the above mixed telomer chlorosulfates is added gradually to 100 grams of sodium hydroxide in 1000 ml. of Water at a temperature of 75 C. over a period of 15 minutes while stirring. Disappearance of the lower chlorosulf-ate layer indicates completion of the reaction.
  • the solution is allowed to cool to room temperature and acidified with 200 milliliters of 50% sulfuric acid, whereupon the organic acid separates out.
  • the entire mixture is extracted with 500 milliliters of diethyl ether and the ethereal layer is washed with water and dried over anhydrous calcium sulfate.
  • This mixture consists of 28% by weight of (ilFa CF2ClCF(OFa)5COONH4 36% by weight of CFzClCF(CFz)5COONH4 24% by weight of i CFzC1OF(CFz)1COONH4 and 12% by weight of CF2C1CF(CF2)9C0ONH4 and has an average chain length in the fluoroalkyl portion of 7.1. This mixture melts at to C.
  • the ether solution is driedover anhydrous calcium sulfate, filtered, and ammonia gas bubbled into the solution to convert the acid into the ammonium salt.
  • the ammonium salt a white solid, was recovered by evaporation of the ether and subsequent drying at 4050 C. There is obtained 114.5 grams (92.8% yield) of the ammonium salt.
  • EXAMPLE 5 --PREPARATION OF i CF201OF(CF2)7COOH from (JFa CF2C1CF(CF2)7OF2OSO2C1
  • the acid F OFQOIOF(OF2)7OOOH is prepared in 90% yield from the chlorosulfa (IJ s OFrOlOF(OF2)7OF2OSOzOl by the procedure described previously.
  • An 81.4 gram sample of i OF2OlCF(OF2)-!COOH is dissolved in 250 milliliters of ethyl ether, and ammonia gas is passed int-o the solution until heat evolution ceases. Some precipitation occurred.
  • the autoclave is sealed and heated with stirring at -175 C. for 2 hours, after which it is cooled to room temperature, opened, and the contents transferred to a separatory funnel while carefully excluding moisture from the product.
  • the reaction mixture separates cleanly into a lower sulfuric acid phase and an upper organic phase.
  • 481 grams of organic material is collected and vacuum distilled.
  • the infrared spectrum of the acid fluoride shows a characteristic strong peak at 5.30 while the carboxylic acid shows characteristic strong bands in the infrared spectrum at 3.20 1, 5.62p. and 6.95
  • the acid fluoride is saponified with a 10% sodium hydroxide solution, then acidified with sulfuric acid and extracted with ether.
  • the dried ethereal layer is combined with the acid co-produced in the reaction and converted to the ammonium salt (CF CF(CF COONH by treatment with ammonia.
  • the yields are essentially quantitative.
  • EXAMPLE 7 PREPARATION OF PERFLUORO 1 l-METHYLDODECANOIC] ACID FROM (CF CF(CF I A 1 gallon stainless steel autoclave equipped with a turbine-type agitator is charged with 562 grams of perfluoro[11-methyldodecyl1iodide, B.P. 137 C. at 18 mm. Hg and 1800 grams of fuming sulfuric acid (35% S0 The autoclave is sealed and heated with stirring at C. for 1.5 hours. The autoclave is cooled to 60 C. and the contents emptied by means of a dip pipe. On further cooling the organic product solidifies, permitting the spent sulfuric acid to be decanted off leaving 503 grams of organic product.
  • EXAMPLE 8 PREPARATION OF $1 3 0193 CF2C1CF CFD COOH FROM OF2ClCF(CF2)aI
  • 612 grams of v i cFioloFwFmr is allowed to react with 1800 grams of fuming sulfuric acid (35% by weight of S0 at a temperature of 135 for three hours.
  • v i cFioloFwFmr is allowed to react with 1800 grams of fuming sulfuric acid (35% by weight of S0 at a temperature of 135 for three hours.
  • the polymerization mixture be 5% of CF ClCF (CF CF I; 3% of CF ClCF (CF CF I Wet by the aqueous polymerization medium. Otherwise, and 2% of CF ClCF (CF CF I where n is greater than F If at tends w 9agu1ate during lymerizanon producmg lumpy, non-umform polymer. In 8 and mostly 1n the range of 9 to 10. 75 view of the difiicultly wettable nature of these fluoropolymers, it is necessary to use a high performance surfactant which produces the maximum lowering of the surface tension of the system.
  • perfluorinated carboxylic acids particularly perfiuorooctanoic acid and its ammonium or alkali metal salts is well known for this purpose.
  • a 2 gallon horizontal polymerizer equipped with a paddle agitator was employed.
  • the polymerizer was evacuated to remove air after which 9.0 grams of ditertiary butyl peroxide polymerization catalyst was injected.
  • the agitator was turned on and the reactor heated to 245 F. at which point it was pressured to 650 lbs/in. gage with vinylidene fluoride monomer. Agitation, temperature and pressure was maintained until 900 grams of the monomer were absorbed over a period of 2%. to 3 hours.
  • Monomer feed was turned oil and the temperature and agitation maintained for 1 additional hour after which the reactor was cooled and emptied, and the liquid containing suspended polymer was filtered through a 60 mesh screen. Any polymer solids remaining in the polymerizer were added to the solids on the screen filter. The non-latex solids (solids removed by the 60 mesh screen plus solids i remaining in the polymerizer) were then dried and weighed.
  • mixtures of surfactants in accordance with the invention having an average chain length in the fluoroalkyl portion essentially the same as that in Runs 3 to 6 inclusive performed well at concentrations ranging from less than one-fourth to about one-fifteenth of that required for the individual surfactants of equivalent average chain length.
  • the mixtures of the invention also have the advantage that they are inherently prepared more cheaply than the individual compounds when employing the telomer iodide precursors for their preparation in the manner previously described.
  • the telomerization reaction tends to produce mixtures of compounds rather than individuals and more economical usage of the telonier product can be obtained by employing the product in ranges of molecular weight than as individual compounds.
  • the mixtures of the invention are not only effective in lower concentrations but are likewise cheaper to prepare than individual compounds of corresponding average chain length.
  • the surfactant mixtures of the invention may be employed for any applications in which a high performance surfactant is required particularly where high chemical stability is also a desideratum.
  • a high performance surfactant is required particularly where high chemical stability is also a desideratum.
  • the surfactant mixtures of the invention may also be employed as leveling agents for waxes, polishes and paints.
  • synergistic mixtures of the invention are obtained directly by starting with appropriate mixtures of fluoroalkyl iodides or fluoroalkyl halosulfates which are then converted to the desired mixtures of acids or salts.
  • the individual compounds such as the individual alkali metal or ammonium salts
  • the synergistic salt mixtures in accordance with this invention are stable, white, waxy, high melting solids (usually over 100 C.) which are water soluble and which are handled and used without difficulty or hazard.
  • the ammonium salt mixtures also show solubility in other polar solvents such as alcohol and ether.
  • the mixtures of acids are usually viscous liquids, but sometimes these acid mixtures are low melting solids.
  • the acid mixtures are also stable, non-hazardous materials and are handled without difficulty. They are soluble in ether and chlorofluorocarbons (e.g. trichlorotrifluoroethane) but have low solubility in benzene, hexane and heptane.
  • a mixture of fluorinated compounds having the general formula II zonrrnoox where Z is selected from the class consisting of fluorine and chlorine; wherein n is an integer from 6 to 13 where the fluoroalkyl group ZC F has a chain length of from 5 to 12 carbon atoms; and where X is selected from the class consisting of hydrogen, alkali metal, ammonium and lower alkyl substituted ammonium; said mixture containing at least three compounds with at least two of the compounds having a fluoroalkyl chain of from 5 to 7 carbon atoms in length and having not more than 8 carbon atoms in the fluoroalkyl group and making up from 60% to 80% by weight of said mixture; the remaining portion of said mixture being made up of at least one of said fluorinated compounds having a fluoroalkyl chain of from 9 to 12 carbon atoms in length.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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US495720A 1963-05-27 1965-10-13 Halogenated carboxylic acids Expired - Lifetime US3311566A (en)

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Application Number Priority Date Filing Date Title
GB1051175D GB1051175A (enrdf_load_stackoverflow) 1963-05-27
FR975857A FR1402173A (fr) 1963-05-27 1964-05-26 Composition d'agents tensio-actifs
DE19641519546 DE1519546B2 (de) 1963-05-27 1964-05-27 Oberflaechenaktive masse
US495720A US3311566A (en) 1963-05-27 1965-10-13 Halogenated carboxylic acids

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US28361263A 1963-05-27 1963-05-27
US495720A US3311566A (en) 1963-05-27 1965-10-13 Halogenated carboxylic acids

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3528924A (en) * 1967-01-24 1970-09-15 Purex Corp Ltd Plastic case desoiling process
DE2641219A1 (de) * 1975-10-30 1977-05-05 Pennwalt Corp Vinylidenfluoridpolymerharz mit verbesserten schmelzfliesseigenschaften
WO2002077046A3 (en) * 2001-03-26 2002-11-28 3M Innovative Properties Co Improved aqueous emulsion polymerization process for producing fluoropolymers
US20040072977A1 (en) * 2001-03-26 2004-04-15 Ralph Kaulbach Aqueous emulsion polymerization process for producing fluoropolymers
US20060128872A1 (en) * 2003-11-17 2006-06-15 3M Innovative Properties Company Aqueous Dispersions of Polytetrafluoroethylene Having a Low Amount of Fluorinated Surfactant

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806866A (en) * 1957-09-17 Hoocxcfcix

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806866A (en) * 1957-09-17 Hoocxcfcix

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3528924A (en) * 1967-01-24 1970-09-15 Purex Corp Ltd Plastic case desoiling process
DE2641219A1 (de) * 1975-10-30 1977-05-05 Pennwalt Corp Vinylidenfluoridpolymerharz mit verbesserten schmelzfliesseigenschaften
WO2002077046A3 (en) * 2001-03-26 2002-11-28 3M Innovative Properties Co Improved aqueous emulsion polymerization process for producing fluoropolymers
US20040072977A1 (en) * 2001-03-26 2004-04-15 Ralph Kaulbach Aqueous emulsion polymerization process for producing fluoropolymers
US7125941B2 (en) 2001-03-26 2006-10-24 3M Innovative Properties Company Aqueous emulsion polymerization process for producing fluoropolymers
US20060128872A1 (en) * 2003-11-17 2006-06-15 3M Innovative Properties Company Aqueous Dispersions of Polytetrafluoroethylene Having a Low Amount of Fluorinated Surfactant
US7294668B2 (en) 2003-11-17 2007-11-13 3M Innovative Properties Company Aqueous dispersions of polytetrafluoroethylene having a low amount of fluorinated surfactant

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DE1519546A1 (de) 1970-02-19
GB1051175A (enrdf_load_stackoverflow)

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