US3684796A - Derivatives of bis-perfluoroalkanoyl-phenylene-diamines - Google Patents

Derivatives of bis-perfluoroalkanoyl-phenylene-diamines Download PDF

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Publication number
US3684796A
US3684796A US13752A US3684796DA US3684796A US 3684796 A US3684796 A US 3684796A US 13752 A US13752 A US 13752A US 3684796D A US3684796D A US 3684796DA US 3684796 A US3684796 A US 3684796A
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Prior art keywords
perfluoro
oil
percent
acid
compounds
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Expired - Lifetime
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US13752A
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English (en)
Inventor
Otto Scherer
Klaus-Dieter Muller
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D203/16—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms
    • C07D203/18—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms by carboxylic acids, or by sulfur or nitrogen analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D203/16—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms
    • C07D203/20—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms by carbonic acid, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/408—Acylated amines containing fluorine atoms; Amides of perfluoro carboxylic acids

Definitions

  • the present invention relates to derivatives of bisperfluoroalkanoyl-phenylene-diamines, more particularly to such of these derivatives which contain an active group in the form of an isocyanate, N,N-ethyleneureidoor N,N-ethylene-amido group at the benzene in which R and R' which may be identical or different, represent a perfluorinated alkyl group having four to 12 carbon atoms and R, represents one of the groups
  • R and R' which may be identical or different, represent a perfluorinated alkyl group having four to 12 carbon atoms and R, represents one of the groups
  • Particularly suitable starting materials are derivatives of m-phenylene-diamine or, preferably, of o-phenylene-diarnine, for example 3,4- or 3,5-diamino-1- nitrobenzene, 3,5- or 3,4-diamino-l-benzoic acid and 3,4- or 3,5-diarnino-benzoic acid methyl ester.
  • Suitable fluorinated carboxylic acids are compounds of the general formula R COOl-I, in which R represents a perfluorinated alkyl group having four to 12, preferably seven to carbon atoms.
  • perfluoroalkanoic acids there may be mentioned by way of example: perfluoro-pentanoic acid, (C F COOH), perfluoro-hexanoic acid (C F COOH), perfluoro-heptanoic acid (C F COOH), perfluoro-octanoic acid (C F, cooh., perfluoro-nonanic acid (C F CO OH), Perfluoro-decanoic acid (C F COOH) or perfluoro-undecanoic acid (C F COOH).
  • the first step in the synthesis of the products of the invention is, preferably, the reaction of the above-mentioned derivatives of mor o-phenylene-diamine with an acid halide, preferably an acid chloride, of the mentioned perfluoro-alkanoic acids.
  • an acid halide preferably an acid chloride
  • the acid chlorides of the perfluoro-alkanoic acids are obtained in known manner with excellent yields from the respective fluorinated carboxylic acid by reaction with suitable chlorinating agents, for example benzo-tri-chloride.
  • acylation of the derivatives of 0- or m-phenylene diarnine may be effected either in the presence of a solvent, for example ethyl acetate or chloroform, and of a base, for example dimethylaniline, at temperatures in the range of from about 10 to 50C, or by melting of the starting materials without additives at about to C.
  • a solvent for example ethyl acetate or chloroform
  • a base for example dimethylaniline
  • the compounds of the invention containing one isocyanate group and corresponding to the formula (VI) NHCORF can be obtained.
  • the isocyanates of the formula (VI) can also be prepared by base phosgenisation.
  • the amine of the formula (V) is introduced at a low temperature, suitably at a temperature in the: range of from about 0 to 20C into a solution of phosgene in an inert solvent and the mixture is slowly heated to a temperature in the range of from 60 to 120C. AFter cooling of the reaction mixture, the crystallized isocyanate can be separated.
  • the bis-acyl-diamino-benzoic acids can be converted in known manner by reaction with, for example thionyl chloride, into the acid chlorides of the formula (I). From these acid chlorides, there are obtained by further reaction with ethylene imine in the presence of a strong base, for example triethylamine, the compounds of the invention which contain an ethylene-amide group and which, if o-phenylenediamine was used as the starting substance, correspond to the formula (IX) NHCORF CH2 (I).
  • a strong base for example triethylamine
  • EXAMPLE 1 a Preparation of perfluoro-octanoic acid chloride 1,600 g (8.2 mols) of benzotrichloride were introduced into a glass flask having a capacity of 4 liters and provided with a stirrer, a reflux condenser, a heatable dropping funnel and a thermometer, and heated to 110C. 1,600 g (3.87 mols) of molten perfluoro-octanoic acid were allowed to run in through the dropping funnel,'in the course of 2 hours and while stirring, while maintaining a reaction temperature of about to C. The hydrogen chloride which escaped through the reflux condenser was absorbed in a vessel filled with water.
  • EXAMPLE 6 a Preparation of 3,4-di-perfluoro-alkanoylamino-1- nitrobenzene 8.4 g of a mixture of 4 parts by weight of perfluorononanoic acid chloride, 88 parts by weight of perfluoro-undecanoic acid chloride and about 8 parts by weight of perfluoro-tridecanoic acid chloride were reacted according to the method described in example 1 (b) with 1.0 g of 3,4-diamino-1-nitrobenzene and 1.8 g of diemethyl-aniline in 100 ml of chloroform.
  • the compounds of the present invention permit the production of oil-, waterand soil-repellent finishes which are resistant to washing and to dry cleaning.
  • Substrates onto which these compounds can be applied are natural and synthetic fibers and filaments and any goods prepared therefrom, furthermore leather, paper and similar substances.
  • the oil-, waterand soil-repellent finishes are produced by applying the compounds in the form of aqueous emulsions, sprays or as solutions in organic solvents such as alcohol, chloroform, tetrahydrofurane or, preferably, acetone, onto the substrate to be provided with the finish and removing the solvent, dispersant or propellant by drying. It is of ad vantage to subject the goods subsequently to a heat treatment, preferably at temperatures of more than C.
  • those compounds of the invention which contain an isocyanate group or an ethylene imide group as the active group.
  • the treatment of the textile materials with these compounds not only imparts onto them oiland water-repellent properties, but makes them also insensitive towards oily and aqueous soiling.
  • soilings produced by coffee, wine, sauces and oils on textile materials that are provided with the finish according to the invention can be completely removed by dabbing off with a small piece of cloth.
  • Dirt which has been rubbed into the fabric is completely removed by a treatment with a suitable solvent, for example one of the solvents usually employed in dry cleaning, because the finish produced with the compounds of the invention reduces the capillary action of the textiles to such an extent that the undesired edge formation, which takes place with textile materials that are not provided with a finish, does not occur.
  • the finishes produced according to the invention show a very good resistance to dry cleaning and to washing, especially if they have been subjected for about 1 to 20 minutes to a heat treatment at elevated temperatures, for example to temperatures in the range of from 120 to 170C.
  • Table 1 gives examples of the good oil-repellent effects of fabrics that had been treated with the compounds of the present invention.
  • specimens of cotton poplin were impregnated with each time 1.0, 0.5, 0.25 and 0.1 percent by weight solutions in acetone of the compounds obtained according to examples 1 (d), 2 and 5 (d), and padded with a squeezing efiect of 100 percent weight increase.
  • the specimens were then dried for 10 minutes at 1 10C and heated for 5 minutes to C.
  • the finishes produced on the fabric were thus 1,0, 0.5 0.25 and 0.1 percent by weight.
  • the values of the oil-repellent effect are the sum of 50 and the proportion, in percent by volume, of n-heptane in the text mixture, according to the following evaluation key:
  • EXAMPLE 8 Specimens of A. cotton poplin and of B. a mixed fabric of 50 parts of polyethylene glycol terephthalate and 50 parts of cotton,
  • the dry cleaning was effected with the aid of carbon tetrachloride for 15 minutes at room temperature.
  • the fabric specimens were tested for their oil-repellent properties according to the test method described in example 7, directly, then after having been subjected once and twice to washing and once to dry cleaning.
  • EXAMPLE 10 A 0.5 percent emulsion of the 3,4-di-perfluoro-octanoylamino-l-N,N-ethylene-ureidobenzene obtained according to example 2 was prepared. For this purpose, the quantity of water required for preparing a 0.5 percent emulsion was stirred into a 2.5 percent solution of this product in acetone, with addition of the sodium salt of perfluoro-octanoic acid as emulsifier in a quantity of 10 percent, referred to the quantity of product initially used.
  • the emulsions obtained were stable over a prolonged period of time and could be combined in excellent manner with other products conventionally used for high quality finishes.
  • R and R which are identical or different, represent a perfluorinated alkyl of four to 12 carbon Fabric Oil-repellent Oil-repellent effect afier atoms Swashmg 2. 3,4-di-perfluoro-octanoyl-amino-1-N,N-ethylene- A 120 100 90 ureido-benzene. B 130 120 120

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Textile Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US13752A 1969-02-25 1970-02-24 Derivatives of bis-perfluoroalkanoyl-phenylene-diamines Expired - Lifetime US3684796A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691909273 DE1909273A1 (de) 1969-02-25 1969-02-25 Derivate von Bis-perfluoralkanoylphenylendiaminen und ihre Verwendung fuer oel-,wasser- und Schmutzabweisende Impraegnierungen

Publications (1)

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US3684796A true US3684796A (en) 1972-08-15

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US13752A Expired - Lifetime US3684796A (en) 1969-02-25 1970-02-24 Derivatives of bis-perfluoroalkanoyl-phenylene-diamines

Country Status (7)

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US (1) US3684796A (enrdf_load_stackoverflow)
BE (1) BE746513A (enrdf_load_stackoverflow)
CH (1) CH260770D (enrdf_load_stackoverflow)
DE (1) DE1909273A1 (enrdf_load_stackoverflow)
FR (1) FR2033043A5 (enrdf_load_stackoverflow)
GB (1) GB1263636A (enrdf_load_stackoverflow)
NL (1) NL7002581A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4537594A (en) * 1983-07-22 1985-08-27 Fogarty P.L.C. Processed feathers

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GR69291B (enrdf_load_stackoverflow) * 1979-06-25 1982-05-13 May & Baker Ltd
AU582346B2 (en) * 1983-09-13 1989-03-23 Minnesota Mining And Manufacturing Company Fluorohydrocarbon sulfonamide compounds and use thereof in treatment of leather, textiles and cellusosic materials
US4539006A (en) * 1983-09-13 1985-09-03 Minnesota Mining And Manufacturing Company Leather treatment

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3250674A (en) * 1965-04-22 1966-05-10 Stauffer Chemical Co Method for controlling insects

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3250674A (en) * 1965-04-22 1966-05-10 Stauffer Chemical Co Method for controlling insects

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4537594A (en) * 1983-07-22 1985-08-27 Fogarty P.L.C. Processed feathers

Also Published As

Publication number Publication date
DE1909273A1 (de) 1970-09-10
BE746513A (fr) 1970-08-25
CH260770D (enrdf_load_stackoverflow)
NL7002581A (enrdf_load_stackoverflow) 1970-08-27
FR2033043A5 (enrdf_load_stackoverflow) 1970-11-27
GB1263636A (en) 1972-02-16

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