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US3147065A - Quaternized halomethylamides - Google Patents

Quaternized halomethylamides Download PDF

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US3147065A
US3147065A US25821A US2582160A US3147065A US 3147065 A US3147065 A US 3147065A US 25821 A US25821 A US 25821A US 2582160 A US2582160 A US 2582160A US 3147065 A US3147065 A US 3147065A
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chloro
cloth
carbon atoms
chloride
treated
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Robert J Koshar
Harvey A Brown
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3M Co
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Minnesota Mining and Manufacturing Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/10—Quaternary compounds
    • 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

  • This invention relates to quaternary ammonium derivatives of halomethylamides and more particlularly to certain new quarternized perfluoroalkyl N-halomethyl carboxylic amides, and to a process for rendering textiles soilresistant and oiland waterrepellent.
  • novel quaternary ammonium derivatives of N- halomethyl amides of the invention contain a quaternary ammonium group attached toa perfluoroalkyl group through an alkylene radical and a carboxyamide radical.
  • the quaternary ammonium group forms the cation of a salt in which the anion is a halide ion.
  • the quaternary ammonium derivatives of N-halomethylamides may also be designated as quaternized N- halomethylamides and the two terms as employed hereinafter are to be considered synonymous.
  • the novel compounds of the invention can be employed as textile finishes to treat wool, nylon, polyacrylate and polyacrylonitrile fibers and the like, and particularly to treat cellulosic materials such as cotton to produce a chemically bonded soil-resistant, waterand oil-repellent finish thereon without thereby altering either the color or tensile strength.
  • Another object is to provide agents by means of which fibrous materials can be rendered oiland water-repellent.
  • Another object of this invention is to provide agents by means of which cellulosic materials and particularly cotton fibers can be rendered lastingly oiland waterrepellent.
  • a further object of this invention is to provide oiland water-repellent cellulosic materials such as cotton cloth.
  • Still another object of the invention is to provide a process for rendering cellulosic materials soil-resistant.
  • R is a perfluoroalkyl group containing 4 to 12 carbon atoms
  • R is a divalent alkylene bridging group selected from the group consisting of:
  • n is an integer from 3 to 12
  • Q is the radical of a tertiary nitrogenous base and X is chlorine or bromine.
  • perfluorocarbon tail or residue contain at least four carbon atoms, and the preferred numher is six to ten.
  • a terminal fluorocarbon chain of this minimum length is required in order to insolubilize and render the end of the molecule both hydrophobic and oleophobic.
  • the perfluor-ocarbon tail structure or residue may include an oxygen atom linking together two perfluorinated carbon atoms, or a nitrogen atom linking together two or three perfluorinated carbon atoms, since these linkages are very stable and do not impair the inert and stable fluorocarbon characteristic of the structure.
  • the R group can be a perfluoroalkyl (C F a perfluorocycloalkyl group (C F or a substituted perfluoroalkyl group (CfiF2 +1)2O or
  • the perfluorocarbon terminal portion of the molecule is inert, non-polar, and is both hydrophobic and oleophobic. It is repellent not only to water but to oils and hydrocarbons.
  • the quaternary ammonium compounds of the invention may be used as the sole component in the treating vehicle or as a component in a complex multi-ingredient formulation. For instance, excellent water and oil repellency and soil resistance is obtained on textile fabrics which are treated simultaneously with the quaternary compound and conventional finishes, such as mildew preventatives, moth resisting agents, crease resistant resins, lubricants, softeners, sizes, flame retardents, antistatic agents, dye fixatives, and water repellents.
  • the quaternary ammonium compound may be present as an ingredient in a wax, starch, casein, elastomer or wet strength resin formulation.
  • the quaternary ammonium compounds of the invention may be used to impart lower surface adhesion values and lower coefficients of friction to substrates. Accordingly, they may also be used as mold release agents, for example, for wooden concrete forms, and related applications.
  • the quaternary ammonium compounds of the invention may be employed in conjunction with other treating agents, such as crease resisting resins, sizes, softeners, and water repellents by concurrent or sequential treatments.
  • treating agents such as crease resisting resins, sizes, softeners, and water repellents by concurrent or sequential treatments.
  • Known treating agents of these classes are as follows.
  • Crease resisting resins Urea-formaldehyde resins, ethylene urea-formaldehyde resins, melamine-formaldehyde resins, triazine-formaldehyde resins, epoxy resins, and polyglycol acetals.
  • Sizes starch, casein, glue, polyvinyl alcohol, polyvinyl acetate, methyl cellulose, carboxymethyl cellulose.
  • Softeners Polyethylene glycols, polyethylene, dimethyl polysiloxanes, amines and amides derived from fatty acids and ethylene oxide condensation products of such amines and amides.
  • Water repellents Waxes, aluminum salts of fatty acids, silicone resins, chromium complexes of fatty acids, N-alkyl amidomethyl pyridinium salts, and melamineformaldehyde resin condensates with amides from fatty acids.
  • R and R have the significance set forth hereinabove, and paraformaldehyde in an inert solvent, such as toluene, benzene and the like, until there is substantially no further absorption of the hydrogen halide.
  • an inert solvent such as toluene, benzene and the like
  • no temperature control is required, although heating from about 25 C. to 100 C. (depending to an extent on the boiling point of the solvent used) may be resorted to insure completion of the reaction.
  • acids are sometimes employed for the cleavage of amides, cleavage does not appear to occur during this reaction even though the strongly acidic hydrogen halides are employed.
  • Another procedure which is very convenient since it avoids the use of hydrogen halides is to react the amide and paraformaldehyde directly with the hydrohalide of the tertiary nitrogenous base, such as pyridine hydrochloride in a suitable solvent such as the amine, e.g. pyridine; and isolation is carried out as described below, adding a further amount of an organic solvent such as ether, if desired.
  • a suitable solvent such as the amine, e.g. pyridine
  • Amides suitable for use in either of the above reactions are, for example:
  • Quaternization can be effected without isolation of the intermediate N-((halomethyl)amide in the inert solvent employed for the reaction, after brief evaporation to remove excess hydrogen halide, or the reaction mixture can be further evaporated and some other solvent, such as anhydrous ether or dioxane, in which the quaternary salt is insoluble, can be added.
  • the desired tertiary organic base or amine is then added in the stoichiometric amount while maintaining the reaction in the range of about 25 C. to about C.
  • any tertiary nitrogenous base which is capable of forming a salt or a quaternary derivative is suitable including for example, trialkyl amines such as trimethylamine, triethanolamine, tributuylamine and tridodecylamines; cycloalkyl amines such as tricyclohexylamine; oralkylamines such as benzyl dimethyl amine; arylamines such as dimethylaniline; and heterocyclic amines such as pyridine, picoline, lutidine, quinoline and the like are suitable.
  • Pyridine is particularly preferred for convenience and economy in the formation of cloth-treating agents as shown above.
  • the compounds are recovered from the reaction mixture by filtration, since the quaternary salts are insoluble in most organic solvents.
  • the quaternized N-halomethylamides of the invention are employed for treating woven or non-woven fibrous materials including wool, cotton, rayon, acetate, nylon, and the like textiles, or paper, leather, wood, felt and similar organic fibrous constructions, and particularly cellulosic materials, by applying thereto the selected quaternary ammonium derivatives, in aqueous medium buffered to a pH in the range of about pH 5.5 to 6.5 and preferably about pH 6, removing any excess, drying at a temperature in the range of about 40 to 100 C., and heating the dried material to about 100 to C. for a period of the order of about 5 to 30 minutes to fix the finish.
  • the material is desirably treated with a mildly alkaline aqueous wash to remove any residual acidic material, and dried.
  • the treatment may be followed by a single aqueous wash before drying, if desired, although this may be omitted since subsequent laundering of the treatment fabric accomplishes the same purpose.
  • the treatment may be termed a finishing treatment, since it is most usefully applied after weaving, forming, dyeing, Weighting, filling or the like have been carried out. Cotton cloth so treated appears to contain residual combined fluorine, indicating that at least a portion of the treating agent has reacted in some fashion, probably through the hydroxyl groups present in the fiber, although this hypothesis is not to be construed as limiting the scope of the invention. 7
  • finishing treatment of the invention can be applied to resin-treated, wrinkle-resistant fabrics without adversely affecting the desirable non-wrinkling feature of such fabrics.
  • a mixture of 35 grams of 10-hendecenoic acid and 98 grams of perfluorooctanesulfonyl chloride is heated under reflux to 130145 C. while slowly adding 1.6 grams of ditertiary butyl peroxide over a period of several hours. Sulfur dioxide is evolved and the mixture darkens. Vacuum distillation yields a white solid boiling at 190204 C./0.5 mm. Hg, and after recrystallization from ethyl ether at subzero temperatures, the ll-perfluorooctyl-lO chlorohendecanoic acid melts at 82-83 C.
  • a solution of 40 parts of the above prepared acid chloride in about 110 parts of anhydrous diethyl ether is saturated for about 25 minutes with anhydrous ammonia while maintaining the temperature below 35 C.
  • hendecanoamide is obtained as white crystals melting 'at about 131 C.
  • the structure is confirmed by the infra red absorption spectrum.
  • the precipitate is collected and recrystallized from acetone, and is recovered as a white powder.
  • the ll-perfluorooctyl- 10-chloro-hendecanamidomethyl pyridinium chloride thus prepared melts (with decomposition) at about 150 C.
  • EXAMPLE 2 By employing other starting materials it is readily possible to prepare any one of the series of compounds of the invention. Thus, when perfiuorobutanesulfonyl chloride is reacted with ethyl vinylacetate under free radical conditions, ethyl beta-chloro-gamma-perfluorobutyl butyrate is produced, which can be hydrolyzed and reduced with Raney nickel catalyst in alkaline solution, to give the corresponding acid.
  • the amide, the N-(bromo-methyl)amide (using hydrogen bromide and paraformaldehyde) and the bromomethylamide is then quaternized with tricyclohexyl amine, the isolated quaternary salt is gamma-perfluorobutylbutyramidomethyl tricyclohexyl ammonium bromide.
  • omegaperfluorododecyltridecanarnidomethyl phenyl dimethyl ammonium bromide is formed by successively reacting perfiuorododecansulfonyl chloride with methyl tridecen- 12-oate-1 followed by reduction and hydrolysis, conversion to the acid chloride and then to the corresponding amide, followed by bromomethylation with HBr and paraformaldehyde and lastly by quaternization with dimethylaniline.
  • the treating solution is prepared by warming sodium acetate trihydrate and the selected treating agent in water at the desired concentrations, which can range from about 0.1 to about 5 percent, at about 30 to 40 C. until solution is effected.
  • the pH of the solution is maintained at about pH 6. It is to be noted that at higher concentration the solution tends to become mucilaginous, resembling a colloidal dispersion.
  • the cloth to be treated is soaked in the solution for 1 minute, removed and squeezed so that a weight of solution approximately equal to 75 to percent of the Weight of the cloth is retained. Under these conditions, the-preferred concentration of treating solution ranges from about 0.5 to about 2 percent.
  • the cloth is then dried for about 10 to 30 minutes at 40 to 100 C- and the treatment is fixed by heating the cloth for about 5 to 30 minutes at from about 100 to C.
  • the fixed, treated cloth is washed for about 30 minutes in an aqueous solution containing 0.1 percent W./V. of sodium lauryl sulfate and 0.2 percent W./v. sodium carbonate, at about 50 to 60 C., rinsed thoroughly and again dried.
  • Other alkaline agents such as dilute alkali metal hydroxides, bicarbonates, ammonium hydroxide and the like can be used instead of alkali metal carbonates, to provide a mildly alkaline washing solution.
  • the effectiveness of the treatments is determined by means of tests for spray rating, oil repellency rating and visual estimation of soil repellency both before further treatment and after one or more cycles of laundering and/ or dry cleaning.
  • laundering is accomplished by Washing in an automatic Washing machine of the stationary tub type, using a detergent under normal household procedures, or by means of a standard 60-minute cycle in a Launder-O-Meter, using chip soap as specified in ASTM D-496. Dry-cleaning is performed by available commercial procedures employing, for example, naphtha or perchloroethylene.
  • Oil repellency of the treated cloth is measured by a severe test in which its resistance to penetration by solutions of mineral oil in heptane is determined. (Higher proportions of heptane bring about quicker penetration.) A material wet by mineral oil alone in less than 3 minutes rates zero, if it is only wet after 3 minutes it rates fifty, while resistance to penetration by a mixture of equal volumes of heptane and mineral oil rates 100. The ratings for resistance for 3 minutes are as follows.
  • Percent heptane Rating 50 70 3O 8O a- 90 100 100+ A rating of or higher indicates a high degree of resistance to staining by salad oil and the like. Dry soil resistance simulates soil repellency of a material under especially exaggerated conditions.
  • a control sample of untreated cloth and the treated sample to be tested are shaken together in a paper bag with about 2 ounces of a standard synthetic soil mixture (having the composition described in the report of Salsbury et al., American Dyestuff Reporter, March 26, 1956, p. 199), then removed and sharply struck against a solid object to remove loosely adherent soil and compared visually with a similarly soiled untreated sample.
  • the ratings are from 0 to 3.
  • the synthetic soil mixture is prepared by blending the following:
  • the blend is placed in a large pan and dried in a forced draft convection oven for 2 hours at 50 C. and then ground in a ball mill.
  • the finely divided material which is produced is stored in a desiccator over calcium chloride or sulfuric acid.
  • Cotton jeans cloth is treated by the procedure outlined above using 2.5 percent of 10-chloro-1l-perfluorooctylhendecanamidomethyl pyridinium chloride (the product of Example 1) and 0.4 percent of sodium acetate trihydrate in water at 32 C. After drying at 6570 C. for 60 minutes, successive samples are cured for times varying from about 2 to about 30 minutes, respectively, at temperatures varying from about to about 190 C. In each case, the sample is then neutralized by washing for 10 minutes at 100 to F. with a 0.1 percent aqueous solution of sodium bicarbonate containing 0.025 percent polyglycolether stearate (available commercially under the Trademark name All), rinsed with clear water at F. for 15 minutes and dried. These samples are rated 100+ for oil repellency and 70+ for water repellency. Washing again with the neutralizing solution used above or laundering for one or two times as described above does not significantly lower these ratings.
  • Solutions containing higher amounts can be used but less economically and as little as 0.1 percent concentration can be used to treat fabrics, which then show oilwaterand soil-repellency before launder-
  • the quaternized N-halornethylamides of Example 2 are used for preparation of treating solutions and cotton cloth is treated therewith as described above it is found that this cloth also shows oiland Water-repellency.
  • treatment of nylon, rayon and woolen fabrics by these procedures confers in them oiland water-repellency.
  • the solutions used for treating fabrics as set forth above can also be applied to paper with slight modifications in procedure to avoid damaging the structure of the paper, which, as is well known, is weakened by treatment with water.
  • the excess of treating solution is removed by permitting the paper to drip dry or by running the web between rolls, while drying and fixing are accomplished by heating the individual sheets or by hot-roll calendering long strips or continuous rolls.
  • the treated paper is oiland water-repellent.
  • EXAMPLE 4 When the treating solution of Example 3 is prepared to contain additionally 10 percent of a melamine-formaldehyde condensate of the type used for providing creaseresistance and 1 percent of a suitable accelerator for advancing the cure of the condensate and is then employed to treat cloth as described above including the drying, curing and neutralizing steps, the cloth is found to be oiland water-repellent and to possess crease resistance.
  • R is perfiuoroalkyl of 4 to 12 carbon atoms
  • X is a halogen of the group consisting of chlorine and bromine
  • R is a divalent radical selected from the group consisting of CH CHCl CH and wherein m is an integer from 1 to and n is an integer from 3 to 12.
  • R is perfiuoroalkyl of 4 to 12 carbon atoms
  • Q is a tertiary nitrogenous organic residue selected from the group consisting of trialkylamino having 3 to about 36 carbon atoms, tricycloalkylamino having about 18 carbon atoms, aralkylamino having about 8 carbon atoms, arylamino having about 8 carbon atoms, pyridino, picolino, lutidono and quinolino
  • X is a halogen of the group consisting of chlorine and bromine
  • R is a divalent radical selected from the group consisting of:
  • R is perfluoroalkyl of 4 to 12 carbon atoms
  • Q is a tertiary nitrogenous organic residue selected from the group consisting of trialkylamino having 3 to about 36 carbon atoms, tricycloalkylamino having about 18 carbon atoms, arlkylamino having about 8 carbon atoms, arylamino having about 8 carbon atoms, pyridino, picolino, lutidino and quinolino
  • X is a halogen of the group consisting of chlorine and bromine
  • R is a divalent radical selected from the group consisting of wherein m is an integer from 1 to 10 and n is an integer from 3 to 12; in aqueous medium buffered to about pH 5.5 to 6.5, drying the treated fibrous materials and heating the dried, treated material to a temperature in the range of about to C. for a period of about 5 to 30 minutes.
  • Rf is perfluoroalkyl of 4 to 12 carbon atoms
  • Q is a tertiary nitrogenous organic residue selected from the group consisting of trialkylamino having 3 to about 36 carbon atoms, tricycloalkylarnino having about 18 carbon atoms, aralkylamino having about 8 carbon atoms, arylamino having about 8 carbon atoms, pyridino, picolino, lutidino and quinolino
  • X is a halogen of the group consisting of chlorine and bromine
  • R is a divalent radical selected from the group consisting of:
  • m is an integer from 1 to 10 and n is an integer from 3 to 12; whereby the fabric contains residual combined fluorine and has oiland water-repellent properties.
  • m is an integer from 1 to 10 and n is an integer from 3 to 12; whereby the fabric contains residual combined fluorine and has oiland water-repellent properties.
  • 7. A cellulosic fabric having oiland water-repellent properties, finished with 11 -perfluorooctane-lOwhlorohendecanamidomethyl pyridinium chloride.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

United States Patent 3,147,065 QUATERNIZED HALOMETHYLAMIDES Robert J. Koshar, Lincoln Township, Washington County, and Harvey A. Brown, East Oakdale Township,
Washington County, Minu., assignors to Minnesota Mining and Manufacturing Company, St. Paul, Minn,
a corporation of Delaware No Drawing. Filed May 2, 1960, Sen'No. 25,821 7 Claims. (Cl. 8-1162) This invention relates to quaternary ammonium derivatives of halomethylamides and more particlularly to certain new quarternized perfluoroalkyl N-halomethyl carboxylic amides, and to a process for rendering textiles soilresistant and oiland waterrepellent.
The novel quaternary ammonium derivatives of N- halomethyl amides of the invention contain a quaternary ammonium group attached toa perfluoroalkyl group through an alkylene radical and a carboxyamide radical. The quaternary ammonium group forms the cation of a salt in which the anion is a halide ion. It will be evident that the quaternary ammonium derivatives of N-halomethylamides may also be designated as quaternized N- halomethylamides and the two terms as employed hereinafter are to be considered synonymous. When the perfluoroalkyl moiety of the compounds of the invention contains from about 4 to about 12 fully fluorinated carbon atoms, it has been found that the novel compounds of the invention can be employed as textile finishes to treat wool, nylon, polyacrylate and polyacrylonitrile fibers and the like, and particularly to treat cellulosic materials such as cotton to produce a chemically bonded soil-resistant, waterand oil-repellent finish thereon without thereby altering either the color or tensile strength.
While it has heretofore been found possible to produce valuable and useful oiland water-repellency in wool and certain synthetic fibers, it has been diflicult to produce lasing effects on the cellulosic fibers. The finishes heretofore developed for this purpose, such as those which employ amidoquaternary amines as described in United States Patent No. 2,303,191, have been relatively easily removed, often by a single laundering operation. They have also required the deposit of relatively large amounts of the treating agent on the fibers, as compared with the compositions of the present invention.
It is an object of this invention to provide certain N- (halomethyl) amides possessing fluorocarbon residues or tails, and their quaternary ammonium derivatives.
Another object is to provide agents by means of which fibrous materials can be rendered oiland water-repellent.
Another object of this invention is to provide agents by means of which cellulosic materials and particularly cotton fibers can be rendered lastingly oiland waterrepellent.
A further object of this invention is to provide oiland water-repellent cellulosic materials such as cotton cloth.
Still another object of the invention is to provide a process for rendering cellulosic materials soil-resistant. Other objects will become apparent hereinafter.
In accordance with the above and other objects of this invention certain novel fluorocarbon-substituted halomethylamides have been discovered which are useful for the production of quaternary ammonium salts containing a perfluorocarbon moiety which may be designated as a tail, or residue. The intermediate halomethylamides are represented by the formula:
while the quaternary amine salts derived therefrom are represented by the formula:
3,147,965 Patented Sept. 1, 1964 ice in which formulae R, is a perfluoroalkyl group containing 4 to 12 carbon atoms, R is a divalent alkylene bridging group selected from the group consisting of:
wherein m is an integer from 1 to 10, and n is an integer from 3 to 12, Q is the radical of a tertiary nitrogenous base and X is chlorine or bromine.
It is important that the perfluorocarbon tail or residue contain at least four carbon atoms, and the preferred numher is six to ten. A terminal fluorocarbon chain of this minimum length is required in order to insolubilize and render the end of the molecule both hydrophobic and oleophobic.
The perfluor-ocarbon tail structure or residue may include an oxygen atom linking together two perfluorinated carbon atoms, or a nitrogen atom linking together two or three perfluorinated carbon atoms, since these linkages are very stable and do not impair the inert and stable fluorocarbon characteristic of the structure. It will be understood that the R group can be a perfluoroalkyl (C F a perfluorocycloalkyl group (C F or a substituted perfluoroalkyl group (CfiF2 +1)2O or The perfluorocarbon terminal portion of the molecule is inert, non-polar, and is both hydrophobic and oleophobic. It is repellent not only to water but to oils and hydrocarbons. It imparts unique surface-active and surfacetreating properties not possessed by corresponding compounds having a hydrocarbon terminal portion, the latter being oleophilic and highly soluble in oils and hydrocarbons, and lacking the property of imparting soil-resistance which is a valuable feature of the compounds of this in vention.
It has been found that the quaternary ammonium derivatives of N-(halomethyl)amides of the invention can be applied to woven and non-woven fabrics as more fully described hereinafter to provide oiland water-repellency with improved resistance to laundering and dry cleaning.
The quaternary ammonium compounds of the invention may be used as the sole component in the treating vehicle or as a component in a complex multi-ingredient formulation. For instance, excellent water and oil repellency and soil resistance is obtained on textile fabrics which are treated simultaneously with the quaternary compound and conventional finishes, such as mildew preventatives, moth resisting agents, crease resistant resins, lubricants, softeners, sizes, flame retardents, antistatic agents, dye fixatives, and water repellents. In the treatment of paper the quaternary ammonium compound may be present as an ingredient in a wax, starch, casein, elastomer or wet strength resin formulation.
In addition to oil and water repellency and soil resistance properties, the quaternary ammonium compounds of the invention may be used to impart lower surface adhesion values and lower coefficients of friction to substrates. Accordingly, they may also be used as mold release agents, for example, for wooden concrete forms, and related applications.
In the treatment of fabrics and fibrous materials, the quaternary ammonium compounds of the invention may be employed in conjunction with other treating agents, such as crease resisting resins, sizes, softeners, and water repellents by concurrent or sequential treatments. Known treating agents of these classes are as follows.
Crease resisting resins: Urea-formaldehyde resins, ethylene urea-formaldehyde resins, melamine-formaldehyde resins, triazine-formaldehyde resins, epoxy resins, and polyglycol acetals.
Sizes: starch, casein, glue, polyvinyl alcohol, polyvinyl acetate, methyl cellulose, carboxymethyl cellulose.
Softeners: Polyethylene glycols, polyethylene, dimethyl polysiloxanes, amines and amides derived from fatty acids and ethylene oxide condensation products of such amines and amides.
Water repellents: Waxes, aluminum salts of fatty acids, silicone resins, chromium complexes of fatty acids, N-alkyl amidomethyl pyridinium salts, and melamineformaldehyde resin condensates with amides from fatty acids.
wherein R and R have the significance set forth hereinabove, and paraformaldehyde in an inert solvent, such as toluene, benzene and the like, until there is substantially no further absorption of the hydrogen halide. As the reaction is not strongly exothermic, no temperature control is required, although heating from about 25 C. to 100 C. (depending to an extent on the boiling point of the solvent used) may be resorted to insure completion of the reaction. Although acids are sometimes employed for the cleavage of amides, cleavage does not appear to occur during this reaction even though the strongly acidic hydrogen halides are employed.
Another procedure which is very convenient since it avoids the use of hydrogen halides is to react the amide and paraformaldehyde directly with the hydrohalide of the tertiary nitrogenous base, such as pyridine hydrochloride in a suitable solvent such as the amine, e.g. pyridine; and isolation is carried out as described below, adding a further amount of an organic solvent such as ether, if desired. The two processes are considered equivalent.
Amides suitable for use in either of the above reactions are, for example:
3-perfiuorobutyl butyramide 3-perfluorodecyl butyramide S-perfluorohendecyl butyramide S-perfluorooctyl caproamide ll-perfluorobutyl undecanamide ll-perfluorooctyl undecanamide 13-perfiuorobutyl tridecanamide l3-perfluoroundecyl tridecanamide l 1- (perfluoro-4-decylcyclohexyl) undecanamide 2-chloro-3-perfiuorobutyl butyramide 2-chloro-3-perfluorooctyl butyramide 2-chloro-3-perfiuorohendecy1 butyramide 4-chloro-5-perfluorooctyl caproamide -chloro-1 1-perfiuorobutylundecanamide 10-chloro-1l-perfluorooctyl undecanamide 12-chloro-13-perfiuorobutyl tridecanamide 12-chloro-13-perfluoroundecyl tridecanamide They are readily available by reaction of the appropriate perfluoroalkanesulfonyl chloride with an ester of the unsaturated aliphatic acid in the presence of a free radical initiator as described in the above cited application followed by direct ammonolysis or by reduction of the chloro atom to hydrogen followed by conversion to the amide by usual procedures.
Quaternization can be effected without isolation of the intermediate N-((halomethyl)amide in the inert solvent employed for the reaction, after brief evaporation to remove excess hydrogen halide, or the reaction mixture can be further evaporated and some other solvent, such as anhydrous ether or dioxane, in which the quaternary salt is insoluble, can be added. The desired tertiary organic base or amine is then added in the stoichiometric amount while maintaining the reaction in the range of about 25 C. to about C. For this purpose any tertiary nitrogenous base which is capable of forming a salt or a quaternary derivative is suitable including for example, trialkyl amines such as trimethylamine, triethanolamine, tributuylamine and tridodecylamines; cycloalkyl amines such as tricyclohexylamine; oralkylamines such as benzyl dimethyl amine; arylamines such as dimethylaniline; and heterocyclic amines such as pyridine, picoline, lutidine, quinoline and the like are suitable. Pyridine is particularly preferred for convenience and economy in the formation of cloth-treating agents as shown above. The compounds are recovered from the reaction mixture by filtration, since the quaternary salts are insoluble in most organic solvents.
Illustrative of the compounds which are thus formed and are suitable as treatments for cloth are the following: 3 (perfiuorobutyl)-butyramidomethyl triethylammonium chloride,
3 (perfluorobutyl)-butyramidomethyl benzyl dimethyl chloride,
3 (perfluorohendecyl)-butyramidomethyl tributyl ammonium bromide,
5 (perfiuorooctyl)-caproarnidomethyl tris(2 hydroxyethyl) ammonium chloride,
ll (perfiuorobutyl) undecanamidomethyl tridodecylammonium bromide,
11 (perfiuorobutyl) undecanamidomethyl phenyl dimethyl ammonium chloride,
13 perfiuorobutyl) tridecanamidomethyl tricyclohexyl ammonium chloride,
13 (perfiuorohendecyl) tridecanamidomethyl lutidinium chloride,
11 (perfluoro-4-ethyl cyclohexyl) undecanamidomethyl triethyl ammonium chloride,
2 chloro 3 (perfluorobutyl)-butyramidomethyl tributyl ammonium chloride,
2 chloro 3 (perfluorodecyl)-butyramidomethyl picolinium bromide,
2 chloro 3 (perfluorohendecyl)-butyramidomethyl diethyl butyl ammonium chloride,
4 chloro 5 (perfluoroctyl)-caproamidomethyl tris(2- hydroxyethyl) ammonium bromide,
10 chloro ll (perfluorobutyl)-undecanamidomethyl methyl ethyl butyl ammonium chloride,
10 chloro 11 (perfiuorooctyl)-undecanamidomethyl phenyl diethyl ammonium chloride,
12 chloro l3 (perfiuorobutyl)-tridecanamidomethyl anisyl dimethyl ammonium bromide,
12 chloro 13 (perfiuorohendecyl)-tridecanamidomethyl phenetyl dimethyl ammonium bromide,
l0-chloro 11 (perfluoro-4-ethyl cyclohexyl) undecanamidomethyl trimethyl ammonium chloride.
The quaternized N-halomethylamides of the invention are employed for treating woven or non-woven fibrous materials including wool, cotton, rayon, acetate, nylon, and the like textiles, or paper, leather, wood, felt and similar organic fibrous constructions, and particularly cellulosic materials, by applying thereto the selected quaternary ammonium derivatives, in aqueous medium buffered to a pH in the range of about pH 5.5 to 6.5 and preferably about pH 6, removing any excess, drying at a temperature in the range of about 40 to 100 C., and heating the dried material to about 100 to C. for a period of the order of about 5 to 30 minutes to fix the finish. Thereafter the material is desirably treated with a mildly alkaline aqueous wash to remove any residual acidic material, and dried. The treatment may be followed by a single aqueous wash before drying, if desired, although this may be omitted since subsequent laundering of the treatment fabric accomplishes the same purpose. The treatment may be termed a finishing treatment, since it is most usefully applied after weaving, forming, dyeing, Weighting, filling or the like have been carried out. Cotton cloth so treated appears to contain residual combined fluorine, indicating that at least a portion of the treating agent has reacted in some fashion, probably through the hydroxyl groups present in the fiber, although this hypothesis is not to be construed as limiting the scope of the invention. 7
It is a surprising feature of cotton fabric treated with these quaternary derivatives that not only is the cloth rendered oiland water-repellent but also it possesses a considerable degree of soil-resistance, that is, it does not become soiled as readily as untreated fabric. Furthermore, when soiled, the fabrics thus treated are readily launderable or dry-cleaned to a clean state, after which they retain their oiland water-repellency. The value of cloth so treated, for example, for childrens clothes, or for uniforms for workers around oily machinery, automotive service men and the like will be readily apparent.
The color of the fabrics treated with the compositions of the invention, and their tensile strength, are not affected by the treatment. The hand of cotton fabrics appears to be improved by the treatment.
It is noted that the finishing treatment of the invention can be applied to resin-treated, wrinkle-resistant fabrics without adversely affecting the desirable non-wrinkling feature of such fabrics.
The procedure for the preparation of the compounds of the invention, and the application of the quaternary ammonium salt derivatives to fabrics, especially cellulosic materials, are more specifically illustrated in the following examples, in which all parts are by weight and all percentages w./v. unless otherwise specified. It will be understood that these examples are illustrative only and show the best mode presently contemplated of practicing the invention, and are not to be construed as limiting as to the scope of the invention.
EXAMPLE 1 1 I-Perfluorooctyl-l O-Chloro-Hendecanamidomethyl Pyridinium Chloride 1l-perfluorooctyl-l0-chlorohendecanoic acid is prepared as follows:
A mixture of 35 grams of 10-hendecenoic acid and 98 grams of perfluorooctanesulfonyl chloride is heated under reflux to 130145 C. while slowly adding 1.6 grams of ditertiary butyl peroxide over a period of several hours. Sulfur dioxide is evolved and the mixture darkens. Vacuum distillation yields a white solid boiling at 190204 C./0.5 mm. Hg, and after recrystallization from ethyl ether at subzero temperatures, the ll-perfluorooctyl-lO chlorohendecanoic acid melts at 82-83 C.
Ai2alysis.Calculated for C I-1 1 60 C, 35.8; F, 50.6; Cl, 5.59. Found: C, 35.7; F, 50.7; Cl, 5.58.
77.3 parts of the above-described acid, which is insoluble in hexane and essentially has a straight carbon chain in the R group, is suspended in about 160 parts of benzene and 26.0 parts of phosphorus pentachloride are added in portions to the mixture over about 5 hours and the mixture heated and stirred for a further 2 hours. The reaction mixture is concentrated under reduced pressure and after distillation of the product (boiling at about 174 C. at 3 mm. Hg), the resultant ll-perfluorooctyllo-chloro-hendecanoyl chloride is obtained as a white solid melting at about 35 C.
Calculated for C H F OCl Found: 35.2% C; 10.6% C1.
A solution of 40 parts of the above prepared acid chloride in about 110 parts of anhydrous diethyl ether is saturated for about 25 minutes with anhydrous ammonia while maintaining the temperature below 35 C.
The precipitate of amide and ammonium chloride is collected, washed with water, and the amide dried and recrystallized from ethanol. 1l-perfluorooctyl-lO-chloro- 34.7% C; 10.8% Cl.
hendecanoamide is obtained as white crystals melting 'at about 131 C. The structure is confirmed by the infra red absorption spectrum.
To a stirred mixture of 5.8 parts (0.5 mole) of pyridine hydrochloride (preferably dried by distillation of benzene therefrom) in 250 parts of pyridine are added gradually 30 parts (0.047 mole) of the above prepared ll-perfluorooctyl-lO-chlorohendecanoamide and 2.2 parts of paraformaldehyde. A slightly exothermic reaction ensues and thereafter the reaction mixture is heated at about C. for 7 hours. On cooling the filtered reaction mixture and diluting with about 150 parts of ether, a precipitate of crude 1l-perfiuorooctyl-l0-chlorohendecanoamido methyl pyridinium chloride is obtained. The precipitate is collected and recrystallized from acetone, and is recovered as a white powder. The ll-perfluorooctyl- 10-chloro-hendecanamidomethyl pyridinium chloride thus prepared melts (with decomposition) at about 150 C.
Calculated for C25H27F17N2OC12.H2OI F; 3.58% N; 9.08% Cl; 2.3% H 0. Found: 38.2% C; 40.2% F; 3.78% N; 9.4% CI; 2.3% H 0.
EXAMPLE 2 By employing other starting materials it is readily possible to prepare any one of the series of compounds of the invention. Thus, when perfiuorobutanesulfonyl chloride is reacted with ethyl vinylacetate under free radical conditions, ethyl beta-chloro-gamma-perfluorobutyl butyrate is produced, which can be hydrolyzed and reduced with Raney nickel catalyst in alkaline solution, to give the corresponding acid. When this acid is successively converted to the corresponding acid chloride, the amide, the N-(bromo-methyl)amide (using hydrogen bromide and paraformaldehyde) and the bromomethylamide is then quaternized with tricyclohexyl amine, the isolated quaternary salt is gamma-perfluorobutylbutyramidomethyl tricyclohexyl ammonium bromide. Similarly, omegaperfluorododecyltridecanarnidomethyl phenyl dimethyl ammonium bromide is formed by successively reacting perfiuorododecansulfonyl chloride with methyl tridecen- 12-oate-1 followed by reduction and hydrolysis, conversion to the acid chloride and then to the corresponding amide, followed by bromomethylation with HBr and paraformaldehyde and lastly by quaternization with dimethylaniline.
EXAMPLE 3 The process for production of soil-resistant, water and oil-repellent cloth using the quaternary derivatives of the compounds of this invention is carried out as follows:
The treating solution is prepared by warming sodium acetate trihydrate and the selected treating agent in water at the desired concentrations, which can range from about 0.1 to about 5 percent, at about 30 to 40 C. until solution is effected. The pH of the solution is maintained at about pH 6. It is to be noted that at higher concentration the solution tends to become mucilaginous, resembling a colloidal dispersion. The cloth to be treated is soaked in the solution for 1 minute, removed and squeezed so that a weight of solution approximately equal to 75 to percent of the Weight of the cloth is retained. Under these conditions, the-preferred concentration of treating solution ranges from about 0.5 to about 2 percent. The cloth is then dried for about 10 to 30 minutes at 40 to 100 C- and the treatment is fixed by heating the cloth for about 5 to 30 minutes at from about 100 to C. The fixed, treated cloth is washed for about 30 minutes in an aqueous solution containing 0.1 percent W./V. of sodium lauryl sulfate and 0.2 percent W./v. sodium carbonate, at about 50 to 60 C., rinsed thoroughly and again dried. Other alkaline agents, such as dilute alkali metal hydroxides, bicarbonates, ammonium hydroxide and the like can be used instead of alkali metal carbonates, to provide a mildly alkaline washing solution.
The effectiveness of the treatments is determined by means of tests for spray rating, oil repellency rating and visual estimation of soil repellency both before further treatment and after one or more cycles of laundering and/ or dry cleaning.
For test purposes, laundering is accomplished by Washing in an automatic Washing machine of the stationary tub type, using a detergent under normal household procedures, or by means of a standard 60-minute cycle in a Launder-O-Meter, using chip soap as specified in ASTM D-496. Dry-cleaning is performed by available commercial procedures employing, for example, naphtha or perchloroethylene.
Determination of water repellency rating is by means of the Spray Test" (Standard Test Method No. 22-52, published in the 1952 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists, vol. 111, p. 136).
Oil repellency of the treated cloth is measured by a severe test in which its resistance to penetration by solutions of mineral oil in heptane is determined. (Higher proportions of heptane bring about quicker penetration.) A material wet by mineral oil alone in less than 3 minutes rates zero, if it is only wet after 3 minutes it rates fifty, while resistance to penetration by a mixture of equal volumes of heptane and mineral oil rates 100. The ratings for resistance for 3 minutes are as follows.
Percent heptane: Rating 50 70 3O 8O a- 90 100 100+ A rating of or higher indicates a high degree of resistance to staining by salad oil and the like. Dry soil resistance simulates soil repellency of a material under especially exaggerated conditions. A control sample of untreated cloth and the treated sample to be tested are shaken together in a paper bag with about 2 ounces of a standard synthetic soil mixture (having the composition described in the report of Salsbury et al., American Dyestuff Reporter, March 26, 1956, p. 199), then removed and sharply struck against a solid object to remove loosely adherent soil and compared visually with a similarly soiled untreated sample. The ratings are from 0 to 3. These correspond to visual estimation to Oas dark as control (untreated cloth sample) 1--slightly less dark than control 2more than about half as dark as control 3-less than about half as dark as control While the ratings are somewhat subjective, and may vary to a certain extent as to the degree of soil involved, it is significant that there is markedly less soiling of samples treated with the compounds of the invention and this property is retained after laundering.
The synthetic soil mixture is prepared by blending the following:
Parts by weight Peat moss 38 Portland cement 17.0 Kaolin clay 17.0 Silica (800 mesh) 17.0 Furnace black (high leading, blue tone, powdered,
Malacco) 1.75 Red iron oxide 0.5 Mineral oil (heavy) 8.75
The blend is placed in a large pan and dried in a forced draft convection oven for 2 hours at 50 C. and then ground in a ball mill. The finely divided material which is produced is stored in a desiccator over calcium chloride or sulfuric acid.
Cotton jeans cloth is treated by the procedure outlined above using 2.5 percent of 10-chloro-1l-perfluorooctylhendecanamidomethyl pyridinium chloride (the product of Example 1) and 0.4 percent of sodium acetate trihydrate in water at 32 C. After drying at 6570 C. for 60 minutes, successive samples are cured for times varying from about 2 to about 30 minutes, respectively, at temperatures varying from about to about 190 C. In each case, the sample is then neutralized by washing for 10 minutes at 100 to F. with a 0.1 percent aqueous solution of sodium bicarbonate containing 0.025 percent polyglycolether stearate (available commercially under the Trademark name All), rinsed with clear water at F. for 15 minutes and dried. These samples are rated 100+ for oil repellency and 70+ for water repellency. Washing again with the neutralizing solution used above or laundering for one or two times as described above does not significantly lower these ratings.
These results show that this material is very effective on cotton and resists the effects of laundering. It is also found to be resistant to dry-cleaning and still exerts some effect even after three dry-cleanings. Analysis of treated samples of cloth indicates that at least about 0.2 percent fluorine should be present in the treated fabric after curing to provide desirable oil- Waterand soil-repellency after laundering. Such an amount is readily furnished by treating solutions containing from about 1.0 to 2.5 percent of the treating agent. Solutions containing higher amounts can be used but less economically and as little as 0.1 percent concentration can be used to treat fabrics, which then show oilwaterand soil-repellency before launder- When the quaternized N-halornethylamides of Example 2 are used for preparation of treating solutions and cotton cloth is treated therewith as described above it is found that this cloth also shows oiland Water-repellency. Likewise, treatment of nylon, rayon and woolen fabrics by these procedures confers in them oiland water-repellency.
The solutions used for treating fabrics as set forth above can also be applied to paper with slight modifications in procedure to avoid damaging the structure of the paper, which, as is well known, is weakened by treatment with water. Thus, the excess of treating solution is removed by permitting the paper to drip dry or by running the web between rolls, while drying and fixing are accomplished by heating the individual sheets or by hot-roll calendering long strips or continuous rolls. The treated paper is oiland water-repellent. When these solutions are painted on wood and dried and heated as above and thereafter washed with a mildly alkaline solution and again dried, it is found that the surface is oiland waterrepellent and resistant to soiling.
EXAMPLE 4 When the treating solution of Example 3 is prepared to contain additionally 10 percent of a melamine-formaldehyde condensate of the type used for providing creaseresistance and 1 percent of a suitable accelerator for advancing the cure of the condensate and is then employed to treat cloth as described above including the drying, curing and neutralizing steps, the cloth is found to be oiland water-repellent and to possess crease resistance.
Thus, other treatments may be employed either concurrently with the treatment as described in Example 3, or, if desired, substantially the same results are obtained by sequential treatment. Thus, when the sample of cloth is treated first with the crease-resistant resin solution described above and subsequently with the solution of Example 3, results are substantially as described for the concurrent treatment.
What is claimed is:
1. A halomethyl amide of the formula:
wherein R; is perfiuoroalkyl of 4 to 12 carbon atoms, X is a halogen of the group consisting of chlorine and bromine, and R is a divalent radical selected from the group consisting of CH CHCl CH and wherein m is an integer from 1 to and n is an integer from 3 to 12.
2. A compound of the formula:
wherein R is perfiuoroalkyl of 4 to 12 carbon atoms, Q is a tertiary nitrogenous organic residue selected from the group consisting of trialkylamino having 3 to about 36 carbon atoms, tricycloalkylamino having about 18 carbon atoms, aralkylamino having about 8 carbon atoms, arylamino having about 8 carbon atoms, pyridino, picolino, lutidono and quinolino, X is a halogen of the group consisting of chlorine and bromine, and R is a divalent radical selected from the group consisting of:
-CH CHCl CH 2 and CH2 n wherein R is perfluoroalkyl of 4 to 12 carbon atoms, Q is a tertiary nitrogenous organic residue selected from the group consisting of trialkylamino having 3 to about 36 carbon atoms, tricycloalkylamino having about 18 carbon atoms, arlkylamino having about 8 carbon atoms, arylamino having about 8 carbon atoms, pyridino, picolino, lutidino and quinolino, X is a halogen of the group consisting of chlorine and bromine, and R is a divalent radical selected from the group consisting of wherein m is an integer from 1 to 10 and n is an integer from 3 to 12; in aqueous medium buffered to about pH 5.5 to 6.5, drying the treated fibrous materials and heating the dried, treated material to a temperature in the range of about to C. for a period of about 5 to 30 minutes.
6. A fabric finished with a compound of the formula:
wherein Rf is perfluoroalkyl of 4 to 12 carbon atoms, Q is a tertiary nitrogenous organic residue selected from the group consisting of trialkylamino having 3 to about 36 carbon atoms, tricycloalkylarnino having about 18 carbon atoms, aralkylamino having about 8 carbon atoms, arylamino having about 8 carbon atoms, pyridino, picolino, lutidino and quinolino, X is a halogen of the group consisting of chlorine and bromine, and R is a divalent radical selected from the group consisting of:
and
and
wherein m is an integer from 1 to 10 and n is an integer from 3 to 12; whereby the fabric contains residual combined fluorine and has oiland water-repellent properties. 7. A cellulosic fabric having oiland water-repellent properties, finished with 11 -perfluorooctane-lOwhlorohendecanamidomethyl pyridinium chloride.
References Cited in the file of this patent UNITED STATES PATENTS 2,216,406 Austin Oct. 1, 1940 2,406,186 Baldwin Aug. 20, 1946 2,409,315 Rigby Oct. 15, 1946 2,412,054 McClellan Dec. 3, 1946 2,750,389 Pingree et a1 June 12, 1956 2,764,602 Ahlbrecht Sept. 25, 1956 2,764,603 Ahlbrecht Sept. 25, 1956 OTHER REFERENCES Noller: Chemistry of Organic Compounds, 2nd ed., p. 241 (Saunders) (1957).

Claims (2)

1. A HALOMETHYL AMIDE OF THE FORMUULA:
5. THE PROCESS FOR RENDERING FIBROUS MATERIALS WATERAND OIL-REPELLENT, WHICH COMPRISES TREATING THE FIBROUS MATERIAL WITH A COMPOUND OF THE FORMULA:
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US3352709A (en) * 1963-01-04 1967-11-14 Boeing Co Method of repelling water from a transparent member
US3428594A (en) * 1961-07-14 1969-02-18 Minnesota Mining & Mfg Resinous composition with fluorinated antimigration agent
US3510494A (en) * 1963-08-12 1970-05-05 Colgate Palmolive Co Certain perfluoro alkanamido-,perfluoro alkanoyloxy-,perfluoroalkyloxy and perfluoro mercapto - quaternary ammonium compounds,the corresponding pyridinium compounds and derivatives thereof
US3622590A (en) * 1969-04-04 1971-11-23 Fmc Corp Certain perfluoroalkyl polyoxyalkylene quaternary ammonium salts and derivatives thereof
US3681413A (en) * 1968-08-01 1972-08-01 Allied Chem Quaternary ammonium compounds
US3734687A (en) * 1969-04-04 1973-05-22 Fmc Corp A fabric finished with a fluorinated quarternized halomethyl ether
US4016209A (en) * 1975-04-23 1977-04-05 Merck & Co., Inc. 3-[N'-(3-Halopropyl)-N-'-methylamino]-N,N,N-trimethyl-1-propanaminium halide and acid addition salts thereof
US4183367A (en) * 1976-06-17 1980-01-15 American Cyanamid Company Enhancing the drying of hair by the use of fluorinated catonic and amphoteric surfactants
US5266076A (en) * 1992-01-24 1993-11-30 E. I. Du Pont De Nemours And Company Fluorinated finishes for aramids
WO2002032855A3 (en) * 2000-10-16 2003-08-21 Ciba Sc Holding Ag Mono- and polyamides of perfluoroalkyl-substituted unsaturated acids

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US2406186A (en) * 1942-01-30 1946-08-20 Ici Ltd Manufacture of surface-active compounds
US2409315A (en) * 1946-10-15 Fltjoroacetamides and their
US2412054A (en) * 1943-10-25 1946-12-03 Du Pont Nylon filaments
US2750389A (en) * 1954-06-24 1956-06-12 Crown Chemical Corp Quaternary ammonium compounds and process of preparing them
US2764603A (en) * 1954-04-21 1956-09-25 Minnesota Mining & Mfg Alkylaminoalkyl-perfluoroamides
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US2409315A (en) * 1946-10-15 Fltjoroacetamides and their
US2216406A (en) * 1938-09-29 1940-10-01 Du Pont Process of treating textiles
US2406186A (en) * 1942-01-30 1946-08-20 Ici Ltd Manufacture of surface-active compounds
US2412054A (en) * 1943-10-25 1946-12-03 Du Pont Nylon filaments
US2764603A (en) * 1954-04-21 1956-09-25 Minnesota Mining & Mfg Alkylaminoalkyl-perfluoroamides
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3428594A (en) * 1961-07-14 1969-02-18 Minnesota Mining & Mfg Resinous composition with fluorinated antimigration agent
US3352709A (en) * 1963-01-04 1967-11-14 Boeing Co Method of repelling water from a transparent member
US3510494A (en) * 1963-08-12 1970-05-05 Colgate Palmolive Co Certain perfluoro alkanamido-,perfluoro alkanoyloxy-,perfluoroalkyloxy and perfluoro mercapto - quaternary ammonium compounds,the corresponding pyridinium compounds and derivatives thereof
US3681413A (en) * 1968-08-01 1972-08-01 Allied Chem Quaternary ammonium compounds
US3622590A (en) * 1969-04-04 1971-11-23 Fmc Corp Certain perfluoroalkyl polyoxyalkylene quaternary ammonium salts and derivatives thereof
US3734687A (en) * 1969-04-04 1973-05-22 Fmc Corp A fabric finished with a fluorinated quarternized halomethyl ether
US4016209A (en) * 1975-04-23 1977-04-05 Merck & Co., Inc. 3-[N'-(3-Halopropyl)-N-'-methylamino]-N,N,N-trimethyl-1-propanaminium halide and acid addition salts thereof
US4183367A (en) * 1976-06-17 1980-01-15 American Cyanamid Company Enhancing the drying of hair by the use of fluorinated catonic and amphoteric surfactants
US5266076A (en) * 1992-01-24 1993-11-30 E. I. Du Pont De Nemours And Company Fluorinated finishes for aramids
WO2002032855A3 (en) * 2000-10-16 2003-08-21 Ciba Sc Holding Ag Mono- and polyamides of perfluoroalkyl-substituted unsaturated acids

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