US3446570A - Novel fluorocarbon derivatives - Google Patents

Novel fluorocarbon derivatives Download PDF

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US3446570A
US3446570A US3446570DA US3446570A US 3446570 A US3446570 A US 3446570A US 3446570D A US3446570D A US 3446570DA US 3446570 A US3446570 A US 3446570A
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reaction
treated
fluorocarbon
water
sulfone
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Richard F Sweeney
Koei-Liang Liauw
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Allied Corp
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    • 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
    • D06M13/405—Acylated polyalkylene polyamines
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2262—Coating or impregnation is oil repellent but not oil or stain release
    • Y10T442/227—Fluorocarbon containing

Definitions

  • this invention relates to reaction products of perfluoroalkyl polyamide compounds with vinyl sulfone compounds, to treatment of textile materials therewith to render the same oleophobic and hydrophobic, and to textile products treated therewith so as to have been rendered oiland water-repellent.
  • fluorochemicals have heretofore been employed in the treatment of textiles to impart thereto oiland water-repellency properties.
  • these fluorochemicals are composed of a perfluoroalkyl chain affixed to an active functional group.
  • the oleophobic and hydrophobic properties of the fluorochemicals are attributed, at least in part, to the inherent low surface energy of the fluorinated surface provided by the prefluoroalkyl chain.
  • the portion of the molecule to which tht perfluoroalkyl chain is affixed provides the physical and chemical bond between the perfluoroalkyl chain and the substrate surface.
  • This bond not only influences the degree of orientation and packing of the perfluoro groups of the perfluoroalkyl chain, and hence, the oiland waterrepellency properties of the fluorochemical, but in particular, determines the durability of the oleophobic and hydrophobic properties obtained.
  • some of the prior art fluorochemicals have obtained acceptable levels of oiland water-repellency, prolonged oiland waterrepellency effects have not been realized using these prior art chemicals. For example, when these chemicals are used for the coating and sizing of textile fabrics and fibers, they are readily removed in laundering and dry cleaning treatments. Apparently, the bonds formed by the active functional group of the fluorochemicals with the treated substrate surface are unstable when the substrate surface is exposed to repeated laundering and dry cleaning treatments.
  • oiland water-repellency agents not only capable of obtaining high levels of oiland water-repellency but also capable of maintaining oleophobic and hydrophobic properties of substrate surfaces treated therewith after their repeated exposure to laundering and dry cleaning treatments.
  • one object of the present invention is the provision of novel fluorocarbon derivatives.
  • Another object is to provide oiland water-repellent compositions of said fluorocarbon derivatives suitable for treating textiles, in particular, cellulosic materials, to impart thereto oleophobic and hydrophobic properties.
  • a still further object is to provide methods for the treatment of textiles employing said fluorocarbon derivatives.
  • a further object is to provide textile materials treated with the fluorocarbon derivatives of the present invention.
  • An additional object of the present invention is the provision of cellulosic materials chemically modified with the novel fluorocarbon derivatives.
  • reaction products of perfluoroalkyl polyamide compounds with vinyl sulfone compounds have been found to impart to textile materials oiland water-repellency properties which properties not only are superior than those characteristic of commercially available oiland water-repellent agents but which are also more durable when cellulosic materials, in particular, treated with the novel reaction products, are exposed to repeated laundering and dry cleaning treatments.
  • certain of the fluorocarbon derivatives of this invention namely, those containing more than one vinyl sulfone radical hereinbelow identified, also may exhibit crease and muss-resistance properties not possessed by the oiland water-repellent agents of the prior art.
  • R is a perfluoroalkyl radical containing of from 3 to 17 carbon atoms
  • x is an integer of from 2 to 6
  • y is an integer of from 1 to 4
  • Z is a member selected from the group consisting of hydrogen, an acyl radical having the formula 0 --JJJR: in which R, has the afore-stated meaning and a vinyl sulfone radical having the formula R R O R R asatattanat in which R is an alkylene, aryl or aralkyl radical, n is 0 to 1 and R is hydrogen, an alkyl, an aryl or a substituted aryl radical and Z' is a member selected from the group consisting of hydrogen, an acyl radical having the formula in which R, n and R have the afore-stated meaning and a radical having the formula -C,Hz;-NZ
  • x and Z have the afore-stated meaning, with the proviso that at least one of Z and Z' is an acyl radical or a radical having the formula H C xH2x1 I'-Z wherein Z is an acyl radical and at least one of Z and Z is a vinyl sulfone radical or a radical having the formula H C;H2;I I-Z wherein Z is a vinyl sulfone radical, said acyl and vinyl sulfone radicals having the afore-stated formulas.
  • R represents the same or a different saturated straight-chain or branched-chain perfluoroalkyl group, preferably containing from 6 to 14 carbon atoms.
  • the alkylene (C H linkage may be a straight-chain or branched-chain group, preferably containing from 2 to 4 carbon atoms.
  • R may be a straightchain or branched-chain alkylene radical containing from 1 to 4 carbon atoms; an aryl radical such as phenyl or naphthyl; or an aralkyl radical such as benzyl, phenethyl or xylyl.
  • R may be an alkyl radical containing from 1 to 6 carbon atoms including methyl, ethyl, propyl, hexyl as well as various isomeric forms thereof; or an aryl radical such as phenyl, naphthyl and substituted derivatives thereof, including ortho, meta-, or para-tolyl; ortho-, metaor para-chlorophenyl and para-nitrophenyl.
  • the vinyl sulfone reactant employed in the preparation of the novel fluorocarbons of the present invention may be substituted or unsubstituted and, when substituted, has only one substituent on each vinyl group.
  • the vinyl sulfone reactant is represented by the formula:
  • vinyl sulfone reactants include divinyl sulfone; dipropenyl sulfone; di-isopropenyl sulfone; distyryl sulfone; bis(1-hexenyl) sulfone; bis- (alpha-ethylvinyl) sulfone; dis(alpha-n-butylvinyl) sulfone; bis(alpha-phenylvinyl) sulfone; 1, 2-bis(vinylsulfonyl) ethane; 1,2-bis(styryl sulfonyl) ethane; 1,4-bis (alpha-ethylvinyl sulfonyl) butane; and 1,4-bis(vinyl sulfonyl) benzene and the like.
  • the sulfone reactant may comprise a compound capable of forming a vinyl sulfone in situ at reaction conditions at which the textile material is treated with the fluorocarbon derivatives of the invention.
  • Typical compounds exhibiting these properties are the bisQS-hydroxyethyl) sulfones, the lower alkanoic carboxylic acid esters thereof and compounds of the class described for example, in the U.S.P. 3,000,- 762 of Sept. 19, 1961.
  • Y and Y is a member selected from the group consisting of hydrogen and an acyl radical having the formula I --Rt in which R, has the afore-stated meaning and Y' is a member selected from the group consisting of hydrogen, an acyl radical having the formula in which x and y have the afore-stated meaning, provided that at ,least one Y and Y is an acyl radical or a radical having the formula in which Y is an acyl radical, said acyl radical having the stated formula, and at least one of Y and Y is hydrogen.
  • the perfiuoroalkyl polyamide reactant herein contemplated is prepared by reaction of a perfluorocarboxylic acid or derivative thereof such as an ester, anhydride or acid halide thereof with a polyalkylene polyamine corresponding to the formula:
  • reaction product obtained as a result of the reaction of the perfiuorocarboxylic acid and polyalkylene polyamine reactants above described, may comprise a single compound conforming to the above-stated structural formula, a mixture of isomers thereof or a reaction mass composed of amide products containing two or more amide functions.
  • the resulting perfiuoroalkyl polyamide is suitable without further purification for direct use as an intermediate in the preparation of the fluorocarbon derivatives of the present invention.
  • the perfiuoroalkyl polyamide may be further purified prior to reaction with the vinyl sulfone reactant, as by distillation or recrystallization using any commonly employed inert organic solvent such as acetonitrile or chloroform.
  • novel fluorocarbon derivatives of this invention are prepared by heating a mixture of the sulfone reactant with the perfiuoroalkyl polyamide starting material, above described. These reactants may be charged in a mol proportion of 1 mol of perfiuoroalkyl polyamide to about 1 to 10, preferably about 2 to 4, mols of sulfone reactant.
  • the reaction temperature and time are dependent upon the particular perfiuoroalkyl polyamide and sulfone reactants involved. The temperature ranges from about 25 C. to 160 0, preferably about 40 C. to C., and the time ranges from about /2 to 4 hours.
  • the reaction may be conducted in the presence of an ineit organic solvent and, when present, the maximum temperature employable is limited only by the reflux temperature of the mixture.
  • the reaction may be effected at superatmospheric pressure, it is preferred to conduct the reaction at atmospheric pressure.
  • the reaction mixture is cooled to ambient conditions and treated with water to effect insolubilization of the fluorocarbon derivative of the present invention.
  • a discrete molecular species of perfiuoroalkyl polyamide is subjected to reaction with the vinyl sulfone reactant, the desired product is obtained as a solid and may be recovered by conventional means, as by filtration.
  • the desired fluorocarbon derivative is obtained as a liquid and may be recovered as the distilland by distillation of the reaction mass.
  • the resulting solid or liquid fluorocarbon product of the reaction is suitable for direct application as an oiland water-repellency agent without further purification.
  • the fluorocarbon product may be further purified prior to treatment therewith of the textile material, as by distillation or recrystallization from any inert organic solvent such as carbon tetrachloride or acetonitrile.
  • the perfluoroalkyl diamide reactant was prepared in the following manner:
  • a solution of 49 grams (0.475 mol) of diethylene triamine in 60 ml. of diethyl ether was placed in a reaction vessel equipped with a dropping funnel, condenser, magnetic stirrer and a calcium chloride drying tube. After chilling the vessel in an ice water bath for a period of about .20 minutes, 34.2 grams (0.079 mol) of n-perfluorooctanoyl chloride was added with stirring to the contents of the vessel during a 30 minute period. After the addition of the n-perfluorooctanoyl chloride reactant was complete, the ice water bath was removed and the stirring was continued at room temperature for a period of 20 min utes. Thereafter, 100 ml.
  • This compound was found to contain 27.01% carbon (theory 26.8%), 1.45% hydrogen (theory 1.23%) and 4.74% nitrogen (theory 4.71%).
  • EXAMPLE 2 Ten grams of 1,9-di-n-perfluorooctanoyl-1,5,9-triazanonane were heated to 80 C. in 30 m1. of dimethylformamide for a few minutes to elfect solution. To this solution 5 ml. of divinyl sulfone were added and the reaction mixture was heated to 90 C. for a period of about 3 hours. The reaction mixture was cooled to room temperature and transferred to a separatory funnel. A total of 30 ml. of water was added to the reaction mixture and a yellow water-insoluble oil layer was formed. The oily layer was extracted with two 25 ml.
  • the prefluoroalkyl diamide reactant was prepared in the following manner:
  • This compound was found to contain 28.63% carbon (theory 28.58%), 59.56% fluorine (theory 61.66%), 1.57% hydrogen (theory 1.63%) and 4.77% nitrogen (theory 4.55%).
  • EXAMPLE 3 Six grams of 1,10-di-n-perfluorooctanoyl-1,4,7,10- tetraazadecane was dissolved in 20 ml. of dimethylforma-mide by heating to C. for a few minutes. To this solution there was added 3 ml. of divinyl sulfone and the mixture was heated to 90 C. for a period of 3 hours. To the reaction product was added 20 ml. of water and a white solid was formed.
  • the perfluoroalkyl diamide reactant was prepared in the following manner:
  • reaction mixture was cooled and 20 ml. of water were added thereto.
  • a water-insoluble oil layer was formed which was extracted with two 25 ml. portions of diethyl ether and the combined ether extracts were dried over magnesium sulfate. After removal of the ether solvent by evaporation under reduced pressure, a viscous yellow oil was obtained.
  • the product oil was subjected to distillation, it began .to decompose at ISO-190 C. and 2-3 millimeters pressure.
  • CHzCHgSOr SOaCH CH2 8 by reaction of 1,l3-di-n-perfluorononanoyl-1,4,7,10,13- pentaazatridecane with l,4-bis(vinylsulfonyl) benzene.
  • the oiland water-repellent compounds of the invention are useful in treating textiles (fabrics and fibers) comprised of natural or synthetic fibers including cotton, nylon, wool, polyethylene terephthalate and polyacrylonitrile.
  • the fluorocarbon derivatives of the invention are especially useful in the treatment of fabrics and fibers comprised of cellulosic and certain cellulosic derivatives which contain cellulosic hydroxyl groups such as cotton, linen, viscose, cupra ammonium rayon, saponified cellulose acetate and salts of cellulose xanthate.
  • the invention is also applicable to the treatment of blends of natural and/or synthetic fibers in cloth, for example, blends containing polyethylene terephthalate, polyacrylonitrile, nylon, cotton and wool.
  • auxiliar agents such as those imparting Water repellency, crease resistance and softening properties may be applied in conjunction with the fluorocarbon chemicals of the invention.
  • other materials such as the surfaces of wood, plastics, glass, paper and metals may be treated with solutions containing the fluorocarbon derivatives of the invention to render the same oiland water-repellent.
  • the fluorocarbon derivatives of the present invention may be applied to the article to be rendered oil-repellent by treating the same with a solution of the repellent and evaporating the solvent. If desired, the treated article may then be cured at an elevated temperature.
  • the concentration of the fluorocarbon derivative 0n the treated 9 article generally may vary from about 0.5% to 10%, preferably 1.0% to 4.0%, based on the weight of the article. Since the solvent used in formulating the oiland water-repellent composition functions essentialy as a carrier for the fluorocarbon derivative, any organic liquid inert to the article to be treated and capable of dissolution of the requisite amount of oiland water-repellency agent may be employed.
  • Acetone, methyl ethyl ketone, acetonitrile and dimethylformamide are illustrative sol- -vents which may be used in preparing the oiland waterrepellent compositions.
  • aqueous emulsions of the oiland water-repellent may be applied onto the articles to be treated by conventional aqueous application methods.
  • the solvent may be evaporated by air drying at room temperature. If it is desired to cure the treated articles the solvent may be evaporated prior to curing or during curing of the oiland water-repellent chemical onto the article.
  • the article treated with a solution of the fluorocarbon derivative is air dried prior to curing for a time sufficient to evaporate essentially all of the solvent. Thereafter, the article having on its surface the oiland water-repellent chemical is cured or heat-set at a temperature of about 100 C. to 160 C. for a time period varying inversely with the temperature, ranging from about 1 second to minutes.
  • the fluorocarbon derivatives of the present invention are preferably applied thereto from an aqueous solution or an aqueous emulsion and in the presence of a basic catalyst.
  • the cellulosic material is moistened with an aqueous solution of the basic catalyst, air dried to remove residual water and then impregnated with an aqueous solution or emulsion of the fluorocarbon derivative of the invention for a time, normally 30 seconds to about 30 minutes, suflicient to retain on the cellulosic material about 1 to preferably 2 to 4% of the fluorocarbon derivative, based on the weight of the cellulosic material.
  • the thusly impregnated cellulosic material is then heated at a temperature of 100 C. to 165 C. for a time period varying inversely with the temperature ranging from about minutes to 30 seconds. After the reaction of the fluorocarbon derivative with the cellulosic material is complete, the chemically modified cellulosic material is washed free of excess catalyst with water and dried.
  • the cellulosic material may be first impregnated with an aqueous solution or emulsion of the fluorocarbon derivative, then treated with an aqueous solution of the basic catalyst, air dried and finally heated to efleet reaction of the fluorocarbon derivative with the cellulosic material.
  • Another modification of the above-described procedure involves premixing the aqueous solution or emulsion of the fluorocarbon derivative together with the basic catalyst prior to impregnation of the cellulosic material.
  • any strong alkaline material which is inert to the sulfone reactant is suitable as a catalyst in effecting the chemical modification of the cellulosic material.
  • the basic catalyst should have a dissociation constant in water of at least 1.8 10- at C.
  • Phosphates, carbonates and hydroxides of alkali metals such as sodium phosphate, sodium carbonate, sodium hydroxide and potassium hydroxide; alkaline-earth metal hydroxides including calcium hydroxide and magnesium hydroxide; and quarternary ammonium hydroxides such as tetraethyl ammonium hydroxide and benzyl trimethyl ammonium hydroxide are illustrative of preferred eflfective basic catalysts.
  • the catalyst concentration is normally dependent upon the strength of the base selected, speed of reaction desired and the nature of the cellulosic material to be treated. In general, catalyst concentrations of about 1 to 20%, preferably 2 to 5%, based on the weight of the solution are satisfactory.
  • Hydrophobic properties of the treated cloth were determined by Method 22-1961 of the American Association of Textile Chemists and Colorists which is described, for example, on pages 152-153 of the Technical Manual and Yearbook of that association for the year 1961. It is to be noted that this method provides for no interpolation of results which are reported as one of the Standard Spray Test ratings which are the six ratings 0, 5-0, 70, 80, 90 and 100.
  • Wash fastness of the treated cloth was determined by Method 61-1961 (Test 11 A) of the American Association of Textile Chemists and Colorists which method is described on pages -106 of the Technical Manual and Yearbook of that association for the year 1961. Conditions employed in this test give results which correlate with the results of five average, careful hand launderings at a temperature of F.
  • y is an integer of from 1 to 4
  • Z is a member selected from the group consisting of hydrogen, an acyl radical having the formula TABLE II Loading on- Waterll Fluorocarbon Treated (percent repellency repellency i derivative xtile by weight) rating rating 7 in which R; has the afo-re-stated meaning and a I W001 1 4.8 90 70 1 1 l h r 1 Dacron 0 120 50 viny su tone radica aving the formula I Nylon 3.3 100 50 f I?
  • Test pieces of the textile cloth (worsted flannel), conditioned ai 507 R.H., were impregnated by total immersion in a 4% acetone solutioii fi of the fluorocarbon derivative, blotted on paper toweling after removal 0 0 from the sample solution and air dried overnight. The impregnated cloths were then heated for 5 minutes in an oven at 155 C.
  • Z is a member secon 1 lens a
  • the weighed cloths were then impregnated lected s group Conslstmg of hydrogen an by total immersion in a 4% acetone solution of the fluorocarbon deriva acyl rad cal havmg the formula tive, air dried for 8 minutes at 50% RH. and weighed to determine the loading (amount of fluorocarbon derivative retained on the cloth).
  • the thusly treated test pieces were then ironed and tested for oiland water- [I repellency.
  • test pieces were condi 1 Pieces of white cotton print cloth (80 x 80 count), conditioned at 50% tioned at 50% R.H., weighed to determine the loading (amount of fluoro R.H., were dipped in a 5% aqueous sodium hydroxide solution for 5 carbon derivative retained on the cloth) and were ironed. The oiland minutes and then air dried for a period of to minutes. The air dried water-repellency ratings of the thusly treated cloths were then detercloths were impregnated by total immersion in a 4% by weight acetone mined before and after subjection oi the treated cloths to standard laun solution of the fluorocarbon, and then blotted on paper toweling after dering and dry cleaning treatments.
  • the impregnated cloths were then 4 Oleophobic and hydrophobic properties of pieces of white cotton heated at a temperature of 150160C. for a period of about 5 minutes in print cloth, commercially finished with the fluorocarbon derivative an oven.
  • the test pieces were rinsed with water, blotted with paper indicated, were determined before and after subjection of the commertoweling and heated for 5 minutes at i160C. Thereafter the test specicially finished cloths to standard laundering and dry cleaning treatmens were conditioned at 50% R.H., weighed to determine the loading ments; in these tests, the loading (amount of fluorocarbon derivative (amount of fluorocarbon derivative retained on the cloth) and were retained on the cloth) was unknown. ironed.
  • the oiland waterrepellency ratings of the thusly treated cloths 5 Rating recorded after Washing equivalent to 30 home launderings. were then determined before and after subjection of the treated cloths 6 Rating recorded after washing equivalent to 20 home launderlngs. to standard laundering and dry cleaning treatments. 7 Rating recorded after dry cleaning equivalent to 18 commercial dry 8 Pieces of white cotton print cloth (80 x 80 count), conditioned at 50% cleanings. R.H., were impregnated by total immersion in a 4% by weight acetone 8 Rating recorded after dry cleaning equivalent to 12 commercial dry solution of the fluorocarbon. The test pieces were blotted with paper cleanings. toweling, then heated at 150C. for 5 minutes in an oven. The test pieces 9 Rating recorded after washing equivalent to 15 home launderings.
  • R has the afore-stated meaning, a vinyl covered a series of novel and valuable compounds which sulfone radical having the formula are not only more eflfective than commercially available oiland water-repellent compositions but also provide O 0 maintenance of oleophobic and hydrophobic properties I I g g 1 l I of substrate surfaces treated therewith after their re- H H peated exposure to laundering and dry cleaning treat- 0 0 ments. d
  • R is a perfluoroalkyl radical containing from 3 to 17 carbon atoms, x is an integer of from 2 to 6 and y is an integer of from 1 to 4.
  • R is a perfiuoroalkyl radical containing from 6 to 14 carbon atoms, x is an integer of from 2 to 4 and y is an integer of from 1 to 4.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

United States Patent Oflice Patented May 2'], 1969 3,446,570 NOVEL FLUOROCARBON DERIVATIVES Richard F. Sweeney, Dover, and Koei-Liang Liauw, Morristown, N.J., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Aug. 25, 1965, Ser. No. 482,597 Int. Cl. D06m 13/08 US. Cl. 8116.2 9 Claims ABSTRACT OF THE DISCLOSURE This invention is directed to a new class of fluorocarbon derivatives and to their application to textile materials to produce oiland water-repellent products. More particularly, this invention relates to reaction products of perfluoroalkyl polyamide compounds with vinyl sulfone compounds, to treatment of textile materials therewith to render the same oleophobic and hydrophobic, and to textile products treated therewith so as to have been rendered oiland water-repellent.
Various fiuorochemicals have heretofore been employed in the treatment of textiles to impart thereto oiland water-repellency properties. In general, these fluorochemicals are composed of a perfluoroalkyl chain affixed to an active functional group. The oleophobic and hydrophobic properties of the fluorochemicals are attributed, at least in part, to the inherent low surface energy of the fluorinated surface provided by the prefluoroalkyl chain. The portion of the molecule to which tht perfluoroalkyl chain is affixed provides the physical and chemical bond between the perfluoroalkyl chain and the substrate surface. This bond not only influences the degree of orientation and packing of the perfluoro groups of the perfluoroalkyl chain, and hence, the oiland waterrepellency properties of the fluorochemical, but in particular, determines the durability of the oleophobic and hydrophobic properties obtained. Although some of the prior art fluorochemicals have obtained acceptable levels of oiland water-repellency, prolonged oiland waterrepellency effects have not been realized using these prior art chemicals. For example, when these chemicals are used for the coating and sizing of textile fabrics and fibers, they are readily removed in laundering and dry cleaning treatments. Apparently, the bonds formed by the active functional group of the fluorochemicals with the treated substrate surface are unstable when the substrate surface is exposed to repeated laundering and dry cleaning treatments. There is, therefore, a great need for oiland water-repellency agents not only capable of obtaining high levels of oiland water-repellency but also capable of maintaining oleophobic and hydrophobic properties of substrate surfaces treated therewith after their repeated exposure to laundering and dry cleaning treatments.
Accordingly, one object of the present invention is the provision of novel fluorocarbon derivatives.
Another object is to provide oiland water-repellent compositions of said fluorocarbon derivatives suitable for treating textiles, in particular, cellulosic materials, to impart thereto oleophobic and hydrophobic properties.
A still further object is to provide methods for the treatment of textiles employing said fluorocarbon derivatives.
A further object is to provide textile materials treated with the fluorocarbon derivatives of the present invention. An additional object of the present invention is the provision of cellulosic materials chemically modified with the novel fluorocarbon derivatives.
These and other objects will be apparent from the following description.
In accordance with the invention, reaction products of perfluoroalkyl polyamide compounds with vinyl sulfone compounds have been found to impart to textile materials oiland water-repellency properties which properties not only are superior than those characteristic of commercially available oiland water-repellent agents but which are also more durable when cellulosic materials, in particular, treated with the novel reaction products, are exposed to repeated laundering and dry cleaning treatments. In addition, certain of the fluorocarbon derivatives of this invention, namely, those containing more than one vinyl sulfone radical hereinbelow identified, also may exhibit crease and muss-resistance properties not possessed by the oiland water-repellent agents of the prior art.
The compounds proposed for use as oiland waterrepellency agents conform to the general formula:
wherein R, is a perfluoroalkyl radical containing of from 3 to 17 carbon atoms, x is an integer of from 2 to 6, y is an integer of from 1 to 4, Z is a member selected from the group consisting of hydrogen, an acyl radical having the formula 0 --JJJR: in which R, has the afore-stated meaning and a vinyl sulfone radical having the formula R R O R R asatattanat in which R is an alkylene, aryl or aralkyl radical, n is 0 to 1 and R is hydrogen, an alkyl, an aryl or a substituted aryl radical and Z' is a member selected from the group consisting of hydrogen, an acyl radical having the formula in which R, n and R have the afore-stated meaning and a radical having the formula -C,Hz;-NZ
in which x and Z have the afore-stated meaning, with the proviso that at least one of Z and Z' is an acyl radical or a radical having the formula H C xH2x1 I'-Z wherein Z is an acyl radical and at least one of Z and Z is a vinyl sulfone radical or a radical having the formula H C;H2;I I-Z wherein Z is a vinyl sulfone radical, said acyl and vinyl sulfone radicals having the afore-stated formulas.
In the above formulas, R, represents the same or a different saturated straight-chain or branched-chain perfluoroalkyl group, preferably containing from 6 to 14 carbon atoms. The alkylene (C H linkage may be a straight-chain or branched-chain group, preferably containing from 2 to 4 carbon atoms. R may be a straightchain or branched-chain alkylene radical containing from 1 to 4 carbon atoms; an aryl radical such as phenyl or naphthyl; or an aralkyl radical such as benzyl, phenethyl or xylyl. R may be an alkyl radical containing from 1 to 6 carbon atoms including methyl, ethyl, propyl, hexyl as well as various isomeric forms thereof; or an aryl radical such as phenyl, naphthyl and substituted derivatives thereof, including ortho, meta-, or para-tolyl; ortho-, metaor para-chlorophenyl and para-nitrophenyl.
Compounds corresponding to the general formula: f l RI([L.1 N(C xHgXN) Y-C 1 I;|,,-I\Y-( i]Eti H2CH2SO2CH=CH2 wherein Rf, x and y have the afore-stated meanings constitute preferred embodiments of the present invention.
The vinyl sulfone reactant employed in the preparation of the novel fluorocarbons of the present invention may be substituted or unsubstituted and, when substituted, has only one substituent on each vinyl group. Illustratively, the vinyl sulfone reactant is represented by the formula:
wherein R, R and n are as previously defined. Specific examples of vinyl sulfone reactants employable herein include divinyl sulfone; dipropenyl sulfone; di-isopropenyl sulfone; distyryl sulfone; bis(1-hexenyl) sulfone; bis- (alpha-ethylvinyl) sulfone; dis(alpha-n-butylvinyl) sulfone; bis(alpha-phenylvinyl) sulfone; 1, 2-bis(vinylsulfonyl) ethane; 1,2-bis(styryl sulfonyl) ethane; 1,4-bis (alpha-ethylvinyl sulfonyl) butane; and 1,4-bis(vinyl sulfonyl) benzene and the like. If desired, the sulfone reactant may comprise a compound capable of forming a vinyl sulfone in situ at reaction conditions at which the textile material is treated with the fluorocarbon derivatives of the invention. Typical compounds exhibiting these properties are the bisQS-hydroxyethyl) sulfones, the lower alkanoic carboxylic acid esters thereof and compounds of the class described for example, in the U.S.P. 3,000,- 762 of Sept. 19, 1961.
The perfiuoroalkyl polyamide reactant suitable for reaction with the above sulfone compounds is characterized by the structural formula:
is a member selected from the group consisting of hydrogen and an acyl radical having the formula I --Rt in which R, has the afore-stated meaning and Y' is a member selected from the group consisting of hydrogen, an acyl radical having the formula in which x and y have the afore-stated meaning, provided that at ,least one Y and Y is an acyl radical or a radical having the formula in which Y is an acyl radical, said acyl radical having the stated formula, and at least one of Y and Y is hydrogen. The perfiuoroalkyl polyamide reactant herein contemplated is prepared by reaction of a perfluorocarboxylic acid or derivative thereof such as an ester, anhydride or acid halide thereof with a polyalkylene polyamine corresponding to the formula:
NHz x k Y X IX Q wherein x and y have the afore-stated meaning and Q is hydrogen or an aminoalkyl radical having the formula C H NH in which x has the afore-stated meaning, as described and claimed in our copending application Ser. No. 482,599 filed of even date. The reaction product, obtained as a result of the reaction of the perfiuorocarboxylic acid and polyalkylene polyamine reactants above described, may comprise a single compound conforming to the above-stated structural formula, a mixture of isomers thereof or a reaction mass composed of amide products containing two or more amide functions. The resulting perfiuoroalkyl polyamide is suitable without further purification for direct use as an intermediate in the preparation of the fluorocarbon derivatives of the present invention. However, if desired, the perfiuoroalkyl polyamide may be further purified prior to reaction with the vinyl sulfone reactant, as by distillation or recrystallization using any commonly employed inert organic solvent such as acetonitrile or chloroform.
The novel fluorocarbon derivatives of this invention are prepared by heating a mixture of the sulfone reactant with the perfiuoroalkyl polyamide starting material, above described. These reactants may be charged in a mol proportion of 1 mol of perfiuoroalkyl polyamide to about 1 to 10, preferably about 2 to 4, mols of sulfone reactant. The reaction temperature and time are dependent upon the particular perfiuoroalkyl polyamide and sulfone reactants involved. The temperature ranges from about 25 C. to 160 0, preferably about 40 C. to C., and the time ranges from about /2 to 4 hours. If desired, the reaction may be conducted in the presence of an ineit organic solvent and, when present, the maximum temperature employable is limited only by the reflux temperature of the mixture. Although the reaction may be effected at superatmospheric pressure, it is preferred to conduct the reaction at atmospheric pressure.
At the conclusion of the reaction, the reaction mixture is cooled to ambient conditions and treated with water to effect insolubilization of the fluorocarbon derivative of the present invention. When a discrete molecular species of perfiuoroalkyl polyamide is subjected to reaction with the vinyl sulfone reactant, the desired product is obtained as a solid and may be recovered by conventional means, as by filtration. However, when mixtures of perfiuoroalkyl polyamides are employed as a starting material in the process, the desired fluorocarbon derivative is obtained as a liquid and may be recovered as the distilland by distillation of the reaction mass.
The resulting solid or liquid fluorocarbon product of the reaction is suitable for direct application as an oiland water-repellency agent without further purification. However, if desired, the fluorocarbon product may be further purified prior to treatment therewith of the textile material, as by distillation or recrystallization from any inert organic solvent such as carbon tetrachloride or acetonitrile.
The following examples relate to the preparation of representative compounds of the present invention but are not intended to be limiting on the scope thereof.
EXAMPLE 1 Solid 1,7 di n perfluorooctanoyl 1,4,7 triazaheptane (2.4 grams) was heated at to C. in 15 ml. of dimethylformamide until all of the solid dissolved. To this solution was added 2 ml. of divinyl sulfone, and the resulting reaction mixture was heated to 140 C. for 3 hours. The reaction product was cooled to room temperature and transferred to a separatory funnel. Thereafter, 25 ml. of water was added and a yellow water-insoluble oil layer was formed. The oily product was extracted with two 25 ml. portions of diethyl ether, the ether extracts were combined, washed with two 25 ml. portions of water and dried over anhydrous magnesium sulfate. The ether was evaporated under vacuum, and the resulting yellow solid residue was recrystallized from carbon tetrachloride. The product of the reaction, 1,7-di-n-perfluorooctanoyl 4- (p vinylsulfonyl) ethyl 1,4,7 triazaheptane, was a solid melting at 9394 C. It is represented by the following structural formula:
This compound was found to contain 28.4% carbon (theory 28.5%), 1.6% hydrogen (theory 1.69%), 4.0% nitrogen (theory 4.16%) .and 2.83% sulfur (theory 3.17%
The perfluoroalkyl diamide reactant was prepared in the following manner:
A solution of 49 grams (0.475 mol) of diethylene triamine in 60 ml. of diethyl ether was placed in a reaction vessel equipped with a dropping funnel, condenser, magnetic stirrer and a calcium chloride drying tube. After chilling the vessel in an ice water bath for a period of about .20 minutes, 34.2 grams (0.079 mol) of n-perfluorooctanoyl chloride was added with stirring to the contents of the vessel during a 30 minute period. After the addition of the n-perfluorooctanoyl chloride reactant was complete, the ice water bath was removed and the stirring was continued at room temperature for a period of 20 min utes. Thereafter, 100 ml. of an 8% aqueous sodium hydroxide solution was added to the reaction mixture and the stirring was continued for an additional 15 minutes. The resulting gelatinous precipitate was filtered at reduced pressure and washed with water. After air drying the precipitate, a yield of 31 grams of 1,7-di-n-perfluorooctanoyl-1,4,7-triazahept'ane, a white solid (melting point 94-97" C.), having the following structural formula was obtained:
This compound was found to contain 27.01% carbon (theory 26.8%), 1.45% hydrogen (theory 1.23%) and 4.74% nitrogen (theory 4.71%).
EXAMPLE 2 Ten grams of 1,9-di-n-perfluorooctanoyl-1,5,9-triazanonane were heated to 80 C. in 30 m1. of dimethylformamide for a few minutes to elfect solution. To this solution 5 ml. of divinyl sulfone were added and the reaction mixture was heated to 90 C. for a period of about 3 hours. The reaction mixture was cooled to room temperature and transferred to a separatory funnel. A total of 30 ml. of water was added to the reaction mixture and a yellow water-insoluble oil layer was formed. The oily layer was extracted with two 25 ml. portions of diethyl ether and the combined ether extract was washed with water and dried over anhydrous magnesium sulfate. After removal of the ether, a pale yellow oil remained which formed a gel on standing. The gel was recrystallized from carbon tetrachloride to yield 1,9-di-n-perfluorooctanoyl-5- (fl-vinylsulfonyl)-ethyl-1,5,9-triazanonane (melting point 81-83" C.) having the following structural formula:
This compound was found to contain 29.6% carbon (theory 30.0%), 1.92% hydrogen (theory 2.02%), 3.7%
(Compound II) 6 nitrogen (theory 4.03%) and 55.8% fluorine (theory 54.8%).
The prefluoroalkyl diamide reactant was prepared in the following manner:
To a solution of 20 grams (0.0467 mol) of methyl-n1 perfluorooctanoate in 25 ml. of diethyl ether, there was added 3.07 grams (0.0235 mol) of di-n-propylene triamine. The resulting solution was heated under reflux temperature for a period of 24 hours. After removal of the solvent under reduced pressure, 16.6 grams of a light yellow oil which solidified in about 30 minutes to give a white sticky solid were obtained. The white sticky solid was recrystallized from acetonitrile to yield 1,9di-nperfluorooctanoyl-1,5,9-triazanonane (a white powder melting at 84-85 C.) having the following structural formula:
This compound was found to contain 28.63% carbon (theory 28.58%), 59.56% fluorine (theory 61.66%), 1.57% hydrogen (theory 1.63%) and 4.77% nitrogen (theory 4.55%).
EXAMPLE 3 Six grams of 1,10-di-n-perfluorooctanoyl-1,4,7,10- tetraazadecane was dissolved in 20 ml. of dimethylforma-mide by heating to C. for a few minutes. To this solution there was added 3 ml. of divinyl sulfone and the mixture was heated to 90 C. for a period of 3 hours. To the reaction product was added 20 ml. of water and a white solid was formed. The solid was Washed with water and air dried to yield 1,10-di-n-perfluorooc.tanoy1-4,7-di (B vinylsulfonyl) ethyl 1,4,7,10 tetraazadecane (melting point 118-121 C.) having the following structural formula:
This compound was found to contain 30.6% carbon (theory 30.7%), 5.46% sulfur (theory 5.48%), 4.99% nitrogen (theory 4.78%) and 48.4% fluorine (theory 48.7%
The perfluoroalkyl diamide reactant was prepared in the following manner:
To a solution of 20 grams (0.0467 mol) of methyl-nperfluorooctanoate in 25 ml. of diethyl ether, there was added 3.4 grams (0.0233 mol) of triethylene tetramine. The resulting solution was heated under reflux temperature for a period of 24 hours. After removal of the solvent under reduced pressure, 20 grams of a white sticky solid were obtained which was subsequently recrystallized from acetonitrile. The product of this reaction was 1,10-di-nperfluorooctanoyl-1,4,7,10-te.traazadecane, a white powder (melting point 89-92 C.) having the following structural formula:
This compound was found to contain 28.51% carbon (theory 28.15%), 62.50% fluorine (theory 60.74%), 1.86% hydrogen (theory 1.72%) and 6.41% nitrogen (theory 5.97
EXAMPLE 4 To a solution of 16 grams (0.037 mol) of methyl perfiuorooctanoate in 20 ml. of diethyl ether there was added 3.5 grams (0.018 mol) of tetraethylenepentamine. The resulting solution was heated to reflux temperature for a period of 3 hours. After removal of the diethyl ether solvent under reduced pressure there remained a viscous yellow oil which did not solidify on standing. This oil was dissolved in 15 ml. of dimethylformamide by heating to C. for a few minutes. To this solution 6 ml. of divinyl sulfone was added and the mixture was heated 7 to 85 C. for a period of 3 hours. Thereafter the reaction mixture was cooled and 20 ml. of water were added thereto. A water-insoluble oil layer was formed which was extracted with two 25 ml. portions of diethyl ether and the combined ether extracts were dried over magnesium sulfate. After removal of the ether solvent by evaporation under reduced pressure, a viscous yellow oil was obtained. When the product oil was subjected to distillation, it began .to decompose at ISO-190 C. and 2-3 millimeters pressure. The product oil, 1,13-di-n-perfluorooctanoyl-4,7,l-tri(fl-vinylsulfonyl) ethyl 1,4,7,l0,13- pentaaz-atridecane, having the following structural formula:
by reaction of l,7-di-nperfluorotetradecanoyl-1,4,7-triazaheptane with dipropenyl sulfone.
by reaction of 1,7-di-n-perfiuorohexadecanoyl-1,4,7-triazaheptane with bis(alpha-ethylvinyl) sulfone.
by reaction of 1,10-di-n-perfluorononanoyl-1,4,7,10-tetraazadecane with distyryl sulfone.
by reaction of 1,l0-di-[(3,5,7-tri-trifluoromethyl) perfluorononanoyl]1,4,7,lO-tetraazadecane with divinyl sulfone.
CHzCHgSOr SOaCH=CH2 8 by reaction of 1,l3-di-n-perfluorononanoyl-1,4,7,10,13- pentaazatridecane with l,4-bis(vinylsulfonyl) benzene.
by reaction of l,l3-di-[(13-trifluoromethyl) perfluorotetradecanoyl] 1,4,7,l0,13 pentaazatridecane with divinyl sulfone.
l I ll omen Fri-Naomi:cram-c armer,
cnzonzsoton om by reaction of 1,1l-di-n-perfluorooctanoyl-1,6,1l-triaza undecane with divinyl sulfone.
by reaction of 1,13 di [(5 trifluoromethyl) perfiuoroheptanoyl] l,5,9,13 tetraazatridecane with divinyl sulfone. (I? (\JHzCHzNHz CF (CFz)t-C-NHOH OHzN-OHzCHzN-CHzCHzN-C-(CFz)sCF CH2CH2S02CH=CH2 H by reaction of 1,lO-n-diperfiuorooctanoyl-7-(Z-aminoethyl)-1,4,7,lO-tetraazadecane with divinyl sulfone.
by reaction, of 1,10-n-diperfluorooctanoyl-7-(Z-n-perfluorooctanamidoethyl) l,4,7,l0 tetraazadecane with divinyl sulfone.
by reaction of 1,10 n diperfluorooctanoyl-7-(Z-aminoethyl)-1,4,7,10-tetraazadecane with divinyl sulfone.
The oiland water-repellent compounds of the invention are useful in treating textiles (fabrics and fibers) comprised of natural or synthetic fibers including cotton, nylon, wool, polyethylene terephthalate and polyacrylonitrile. The fluorocarbon derivatives of the invention are especially useful in the treatment of fabrics and fibers comprised of cellulosic and certain cellulosic derivatives which contain cellulosic hydroxyl groups such as cotton, linen, viscose, cupra ammonium rayon, saponified cellulose acetate and salts of cellulose xanthate. The invention is also applicable to the treatment of blends of natural and/or synthetic fibers in cloth, for example, blends containing polyethylene terephthalate, polyacrylonitrile, nylon, cotton and wool. If desired, auxiliar agents such as those imparting Water repellency, crease resistance and softening properties may be applied in conjunction with the fluorocarbon chemicals of the invention. In addition, other materials such as the surfaces of wood, plastics, glass, paper and metals may be treated with solutions containing the fluorocarbon derivatives of the invention to render the same oiland water-repellent.
The fluorocarbon derivatives of the present invention may be applied to the article to be rendered oil-repellent by treating the same with a solution of the repellent and evaporating the solvent. If desired, the treated article may then be cured at an elevated temperature. The concentration of the fluorocarbon derivative 0n the treated 9 article generally may vary from about 0.5% to 10%, preferably 1.0% to 4.0%, based on the weight of the article. Since the solvent used in formulating the oiland water-repellent composition functions essentialy as a carrier for the fluorocarbon derivative, any organic liquid inert to the article to be treated and capable of dissolution of the requisite amount of oiland water-repellency agent may be employed. Acetone, methyl ethyl ketone, acetonitrile and dimethylformamide are illustrative sol- -vents which may be used in preparing the oiland waterrepellent compositions. Alternatively, aqueous emulsions of the oiland water-repellent may be applied onto the articles to be treated by conventional aqueous application methods.
The solvent may be evaporated by air drying at room temperature. If it is desired to cure the treated articles the solvent may be evaporated prior to curing or during curing of the oiland water-repellent chemical onto the article. Preferably, the article treated with a solution of the fluorocarbon derivative is air dried prior to curing for a time sufficient to evaporate essentially all of the solvent. Thereafter, the article having on its surface the oiland water-repellent chemical is cured or heat-set at a temperature of about 100 C. to 160 C. for a time period varying inversely with the temperature, ranging from about 1 second to minutes.
When cellulosic materials are to be rendered oiland Water-repellent, the fluorocarbon derivatives of the present invention are preferably applied thereto from an aqueous solution or an aqueous emulsion and in the presence of a basic catalyst. The cellulosic material is moistened with an aqueous solution of the basic catalyst, air dried to remove residual water and then impregnated with an aqueous solution or emulsion of the fluorocarbon derivative of the invention for a time, normally 30 seconds to about 30 minutes, suflicient to retain on the cellulosic material about 1 to preferably 2 to 4% of the fluorocarbon derivative, based on the weight of the cellulosic material. The thusly impregnated cellulosic material is then heated at a temperature of 100 C. to 165 C. for a time period varying inversely with the temperature ranging from about minutes to 30 seconds. After the reaction of the fluorocarbon derivative with the cellulosic material is complete, the chemically modified cellulosic material is washed free of excess catalyst with water and dried.
Various modifications of the above-described treatment may also be employed without departing from the spirit of the invention. For example, the cellulosic material may be first impregnated with an aqueous solution or emulsion of the fluorocarbon derivative, then treated with an aqueous solution of the basic catalyst, air dried and finally heated to efleet reaction of the fluorocarbon derivative with the cellulosic material. Another modification of the above-described procedure involves premixing the aqueous solution or emulsion of the fluorocarbon derivative together with the basic catalyst prior to impregnation of the cellulosic material. Chemical modification of the cellulosic material under anhydrous conditions, as in the presence of solvents capable of penetrating cellulosic fibers such as benzene, chloroform, dioxane and acetone, constitutes still another variation of the afore-described procedures.
Any strong alkaline material which is inert to the sulfone reactant is suitable as a catalyst in effecting the chemical modification of the cellulosic material. In general, the basic catalyst should have a dissociation constant in water of at least 1.8 10- at C. Phosphates, carbonates and hydroxides of alkali metals such as sodium phosphate, sodium carbonate, sodium hydroxide and potassium hydroxide; alkaline-earth metal hydroxides including calcium hydroxide and magnesium hydroxide; and quarternary ammonium hydroxides such as tetraethyl ammonium hydroxide and benzyl trimethyl ammonium hydroxide are illustrative of preferred eflfective basic catalysts. The catalyst concentration is normally dependent upon the strength of the base selected, speed of reaction desired and the nature of the cellulosic material to be treated. In general, catalyst concentrations of about 1 to 20%, preferably 2 to 5%, based on the weight of the solution are satisfactory.
Tests relating to the evaluation of typical fluorocarbon derivative compositions of the present invention as oiland Water-repellency agents were conducted. In addition, oiland water-repellency durabilities of textile test specimens treated with fluorocarbon derivative compositions of this invention were compared with oiland water-repellency durabilities of textile test specimens treated with commercially available oiland water-repellent fluorocarbon derivative compositions.
The procedure employed in determining the oil-repellency ratings is described, for example, on pages 323-4 of the April 1962 edition of the Textile Research Journal. This procedure involves gently placing on the treated fabric drops of mixtures of mineral oil (Nujol) and nheptane in varying proportions. The drops are allowed to stand on the treated fabric undisturbed for 3 minutes. After the 3 minute time period the wetting and penetration of the fabric is visually observed. Referring to following Table I, the number corresponding to the mixture containing the highest percentage of heptane which does not penetrate or wet the fabric is considered to be the oil-repellency rating of the treated fabric.
TABLE I Percent mineral Oil-repellency rating oil Percent nheptane i 0 N o holdout to mineral oil Nujol Saybolt viscosity 360/390 at 100 F. Specific gravity 0.880/ 0.900 at 60 F. Percent by volume at 20 C.
2 Heptane B.P. 9899 0. Percent by volume at 20 C.
When typical oily staining materials are dropped onto treated fabrics and subsequently blotted off, those fabrics with an oil-repellency rating of 50-70 will exhibit only fair resistance to staining; those fabrics with an oil-repellency rating of -90 will have good resistance to staining; and those with an oil-repellency rating of 100 and up will give excellent resistance.
Hydrophobic properties of the treated cloth were determined by Method 22-1961 of the American Association of Textile Chemists and Colorists which is described, for example, on pages 152-153 of the Technical Manual and Yearbook of that association for the year 1961. It is to be noted that this method provides for no interpolation of results which are reported as one of the Standard Spray Test ratings which are the six ratings 0, 5-0, 70, 80, 90 and 100.
Wash fastness of the treated cloth was determined by Method 61-1961 (Test 11 A) of the American Association of Textile Chemists and Colorists which method is described on pages -106 of the Technical Manual and Yearbook of that association for the year 1961. Conditions employed in this test give results which correlate with the results of five average, careful hand launderings at a temperature of F.
The effect of repeated dry cleaning of the treated cloth was determined by Method 85-1060'1 of the American Association of Textile Chemists and Colorists which method is described on pages 87-88 of the Technical Manual and Yearbook of that association for the year 1961. This test is based on an extensive series of interlaboratory tests which showed there is good correlation between the test and 3 commercial dry cleanings in a 4% charged system using perchloroethylene solvent.
The results obtained are set forth in Tables II and III below:
6, y is an integer of from 1 to 4, Z is a member selected from the group consisting of hydrogen, an acyl radical having the formula TABLE II Loading on- Waterll Fluorocarbon Treated (percent repellency repellency i derivative xtile by weight) rating rating 7 in which R; has the afo-re-stated meaning and a I W001 1 4.8 90 70 1 1 l h r 1 Dacron 0 120 50 viny su tone radica aving the formula I Nylon 3.3 100 50 f I? i f 1 Test pieces of the textile cloth (worsted flannel), conditioned ai 507 R.H., were impregnated by total immersion in a 4% acetone solutioii fi of the fluorocarbon derivative, blotted on paper toweling after removal 0 0 from the sample solution and air dried overnight. The impregnated cloths were then heated for 5 minutes in an oven at 155 C. Thereafter the e51 piec(es were crfirglitionedbat Bill, w ei h d to t lileteiiniiklse 1n which R 1s an alkylene, an aryl or an aralkyl e 0a mg amoun o uorocar on eriva we re ame on e c o ironed and tested for oiland water-repellency. radlcal 1S 0 to 1 i R 15 hydfogen, an alkyl 2 gr t piiacezssg tgeextile coth ((islleer clacroii Biid lly1l;0l'l tango? or substituted aryl radical and Z is a member secon 1 lens a were ippe in ace one or minu es, en ie for 8 minutes and weighed. The weighed cloths were then impregnated lected s group Conslstmg of hydrogen an by total immersion in a 4% acetone solution of the fluorocarbon deriva acyl rad cal havmg the formula tive, air dried for 8 minutes at 50% RH. and weighed to determine the loading (amount of fluorocarbon derivative retained on the cloth). The thusly treated test pieces were then ironed and tested for oiland water- [I repellency. 2O C--R TABLE III Oil- Water- Oil- Waterrepellency repellency repellency repellency Loading Oil- Waterrating rating rating rating Fluoro- (Percent repcllency repellency (after laun- (after laun- (after dry (after dry carbon derivative by weight) rating rating dering) dering) cleaning) cleaning) I 4. 0 2 130 Z 70 5 130 140 100 4 110 4 70 G 0 110 70 1 A commercially available oiland water-repellent. and heated for 5 minutes at 150C. Thereafter the test pieces were condi 1 Pieces of white cotton print cloth (80 x 80 count), conditioned at 50% tioned at 50% R.H., weighed to determine the loading (amount of fluoro R.H., were dipped in a 5% aqueous sodium hydroxide solution for 5 carbon derivative retained on the cloth) and were ironed. The oiland minutes and then air dried for a period of to minutes. The air dried water-repellency ratings of the thusly treated cloths were then detercloths were impregnated by total immersion in a 4% by weight acetone mined before and after subjection oi the treated cloths to standard laun solution of the fluorocarbon, and then blotted on paper toweling after dering and dry cleaning treatments. removal from the sample solution. The impregnated cloths were then 4 Oleophobic and hydrophobic properties of pieces of white cotton heated at a temperature of 150160C. for a period of about 5 minutes in print cloth, commercially finished with the fluorocarbon derivative an oven. The test pieces were rinsed with water, blotted with paper indicated, were determined before and after subjection of the commertoweling and heated for 5 minutes at i160C. Thereafter the test specicially finished cloths to standard laundering and dry cleaning treatmens were conditioned at 50% R.H., weighed to determine the loading ments; in these tests, the loading (amount of fluorocarbon derivative (amount of fluorocarbon derivative retained on the cloth) and were retained on the cloth) was unknown. ironed. The oiland waterrepellency ratings of the thusly treated cloths 5 Rating recorded after Washing equivalent to 30 home launderings. were then determined before and after subjection of the treated cloths 6 Rating recorded after washing equivalent to 20 home launderlngs. to standard laundering and dry cleaning treatments. 7 Rating recorded after dry cleaning equivalent to 18 commercial dry 8 Pieces of white cotton print cloth (80 x 80 count), conditioned at 50% cleanings. R.H., were impregnated by total immersion in a 4% by weight acetone 8 Rating recorded after dry cleaning equivalent to 12 commercial dry solution of the fluorocarbon. The test pieces were blotted with paper cleanings. toweling, then heated at 150C. for 5 minutes in an oven. The test pieces 9 Rating recorded after washing equivalent to 15 home launderings. were dipped in a 5% aqueous sodium hydroxide solution for 5 minutes, it! Rating recorded after dry cleaning equivalent to 6 commercial dry air dried for 30 minutes, and then heated at 150C. for 5 minutes in an cleanings. oven. The test pieces were rinsed with water, blotted with paper toweling From the foregoing it is apparent that we have disin which R; has the afore-stated meaning, a vinyl covered a series of novel and valuable compounds which sulfone radical having the formula are not only more eflfective than commercially available oiland water-repellent compositions but also provide O 0 maintenance of oleophobic and hydrophobic properties I I g g 1 l I of substrate surfaces treated therewith after their re- H H peated exposure to laundering and dry cleaning treat- 0 0 ments. d
e val-1911s clianges and nio'dlficanons i be ma in which R, n and R have the afore-stated meaning in the invention without departing from the spirit thereof, and a r a die all having the formula it is intended that all matter contained in the above descripion shall be interpreted as illustrative and not in 1 1 a limiting sense. 0 xHh'-NZ We claim: 1. A textile treated with a compound having the structural formula: in which x and Z have the afore-stated meaning, with the proviso that at least one of Z and Z is an I? a 1. acyl radical or a radical having the formula R;(N CzHhN -C din-N-Z H wherein R is a erfluoroalk l radical containing from i P y -o,Hn-NZ 3 to 17 carbon atoms, at is an integer of from 2 to wherein Z is an acyl radical and at least one of Z and Z is a vinyl sulfone radical or a radical having the formula wherein Z is a vinyl sulfone radical, said acyl and vinyl sulfone radicals having the afore-stated formulas.
2. A textile treated with a compound having the structural formula:
wherein R; is a perfluoroalkyl radical containing from 3 to 17 carbon atoms, x is an integer of from 2 to 6 and y is an integer of from 1 to 4.
3. A textile treated with a compound having the structural formula:
wherein R; is a perfiuoroalkyl radical containing from 6 to 14 carbon atoms, x is an integer of from 2 to 4 and y is an integer of from 1 to 4.
4. A textile treated with a compound having the structural formula:
5. A textile treated with a compound having the structural formula:
14 6. A textile treated with a compound having the structural formula:
7. A textile treated with a compound having the structural formula:
References Cited UNITED STATES PATENTS 4/ 1964 Wear.
9/ 1966 Mackenzie.
3/ 1966 Hauptschein. 11/ 1967 Gagliari.
NORMAN G. TORCHIN, Primary Examiner.
I. E. CALLAGHAN, Assistant Examiner.
US. Cl. X.R.
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US20080039605A1 (en) * 2006-08-08 2008-02-14 Weiming Qiu Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide

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US3719448A (en) * 1969-07-18 1973-03-06 Us Agriculture Organo-phosphorus compounds containing perfluoroalkyl radicals and their application to cellulosic textiles
US20080039605A1 (en) * 2006-08-08 2008-02-14 Weiming Qiu Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
US7754838B2 (en) 2006-08-08 2010-07-13 E.I. Du Pont De Nemours And Company Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
US8178638B2 (en) 2006-08-08 2012-05-15 E.I. Du Pont De Nemours And Company Poly(meth)acrylamides and poly(meth)acrylates containing fluorinated amide
US8389657B2 (en) 2006-08-08 2013-03-05 E. I. Du Pont De Nemours And Company Poly(meth)acrylamides and poly(meth)acrylates containing flourinated amide

Also Published As

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DE1594888A1 (en) 1969-09-18
GB1124538A (en) 1968-08-21
US3595886A (en) 1971-07-27
FR1509946A (en) 1968-01-19
US3420697A (en) 1969-01-07
NL6611903A (en) 1967-02-27

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