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US3322490A - Textiles reacted with methylol perfluoroalkanamides - Google Patents

Textiles reacted with methylol perfluoroalkanamides Download PDF

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Publication number
US3322490A
US3322490A US301597A US30159763A US3322490A US 3322490 A US3322490 A US 3322490A US 301597 A US301597 A US 301597A US 30159763 A US30159763 A US 30159763A US 3322490 A US3322490 A US 3322490A
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US
United States
Prior art keywords
water
oil
textile
soil
fabrics
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US301597A
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English (en)
Inventor
Gagliardi Domenick Donald
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colgate Palmolive Co
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Colgate Palmolive Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to US301597A priority Critical patent/US3322490A/en
Priority to DE1469289A priority patent/DE1469289C3/de
Priority to CH1024064A priority patent/CH461428A/de
Priority to FR984796A priority patent/FR1534665A/fr
Priority to GB32677/64A priority patent/GB1058818A/en
Application granted granted Critical
Publication of US3322490A publication Critical patent/US3322490A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/433—Amino-aldehyde resins modified by phosphorus compounds by phosphoric acids
    • 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 class of water-proofing materials generally comprises a mixture containing:
  • a paralfin wax or mixtures of vegetable wax esters such as carnauba, candelilla, or sugar cane wax are examples of vegetable wax esters such as carnauba, candelilla, or sugar cane wax.
  • An aluminum or zirconium salt usually the formate or acetate.
  • the primary function of the salt is to insolubilize the glue and other emulsifiers after the emulsion is deposited on the fabric.
  • thermosetting nor fiber reaction occurs when textiles are coated with such products, the treated textile is non-durable to washing and dry cleaning.
  • water repellency for rainwear fabrics such mixtures provide fabrics with a fair degree of spot and stain resistance to water-borne chromophoric materials.
  • This material was octadecyloxymethyl pyridinium chloride, a quaternary ammonium compound made by the chlorornethylation of octadecanol, followed by quaternization with pyridine to yield a product having a composition represented by the formula
  • This compound unlike other quaternaries, is unstable and under acid conditions reacts with surfaces containing active hydrogen, e.g., the hydrogen of a hydroxyl group in cellulose fibers. If the cellulose molecules be represented by Z(OH) then the reaction can be considered to be summarized by the equation:
  • Fabrics treated with such a compound are durably water repellent, are porous, soft, and have the appearance of untreated fabrics.
  • Velan type material A major improvement of the Velan type material was made when the stearamidomethyl analog of Velan (In-H350 ONHOHQN/ commercially known as Zelan and Norane R was produced.
  • the advantage of the stearamide product is greater initial water repellency and greater durability to washing. Such products are still among the forefront of the leaders in rainwear fabric finishes.
  • 3M made a product known as PC- 208 available as a finish. It is generally believed that this finishing material is a perfluorosulfonamide having a composition corresponding to the formula where x is an integer in the range of 3 to 13, R is methyl, ethyl, propyl, butyl, amyl, hexyl, R" is an alkylene radical having 1 to 12 carbon atoms and R is hydrogen, methyl, or ethyl.
  • WATER REPELLENCY Resistance to Wetting AATCC Standard Test Method 22-1952 This test is applicable to any textile fabric. It measures the resistance of fabrics to wetting by a water spray and the results depend primarily on the degree of hydrophobicity inherent in the fibers and yarns and subsequent treatments to which the fabric is subjected. Water is sprayed against the taut surface of a test specimen. Evaluation of the wetted pattern is readily brought about by comparing the wetted pattern with standard wetting pattern pictures:
  • test specimens of minimum size of 7" x 7" are conditioned at 70 F. and 65 percent relative humidity for a minimum of four hours before testing.
  • test specimen fastened securely and wrinkle-free in a metal hoop having a diameter of 6 inches, is placed and centered 6 inches under a standard spray nozzle at an angle of 45 to the horizontal.
  • Two hundred and fifty milliliters of water at :2" F. is poured into a funnel attached above the spray nozzle.
  • the spray lasts 25 to 30 seconds at the end of which time the hoop is taken by one edge and the opposite edge tapped smartly once against a solid object with the wet side facing the solid; this procedure is repeated with the hoop reversed 180.
  • the standard oil-heptane mixtures are contained in small stoppered medicine-dropper bottles. A drop of each mixture of Nujol and heptane is placed on the fabric. The appearance of the test oil is observed through the drop. Note is made whether wetting or penetration occurs. The number corresponding to that mixture containing the highest percentage of heptane which does not penetrate or wet the fabric after three minutes is considered the oil repellency rating of the system.
  • the change in the optical refractivity of the drop is often an indication of wetting. In some cases wetting can be better determined by observing the other side of the fabric. In some cases reported hereinafter the term 0+ has been used to indicate a modicum of resistance to wetting by oil.
  • OILY PARTICULATE SOIL REPELLENCY GCC Dry Soil Test Fifteen to twenty 6" x 8" numbered speciments (normally 80 x 80 cotton), including at least one untreated control, are tumbled for thirty minutes with 10 percent of Cyanamid Soil based on the weight of the fabric. The tumbling is carried out in a 5 liter capacity Five Minute Home Cleaner at 44 rpm; six No. 8 neoprene rubber stoppers are distributed among the speciments to increase the mechanical action. At the end of the tumbling, the specimens are removed and each shaken separately up and down fifteen times by hand to remove surface dirt.
  • the specimens are then cut in two (to produce two 4" x 6" pieces). One-half is washed with 50 grams of Fab in a cotton cycle with a S-pound dummy load, then hung to dry and lightly ironed under a clean cotton cloth.
  • the degree of soiling is determined with a Photovolt Reflectance Meter (Tri Blue Filter). Six reading per specimen are made and the arithmetic average reported.
  • Cyanamide Soil described below is the same as that recommended by Minnesota Mining and Manufacturing Co.
  • the following dry ingredients are blended thoroughly, dried in a forced draft convection over for eight hours at 50 C., then milled for twenty-five hours with ceramic balls and stored in a polyethylene bag.
  • Cyanamide Soil Material Percent by weight Peat moss 38 Cement 17 Kaolin clay 1 17 Silica, 200 mesh 2 17 Furnace black 1.75 Red iron oxide 4 0.50 Mineral oil 8.75
  • Q is a perfluoroalkyl group having three to twentyone carbon atoms and seven to forty-three hydrogen atoms of which at least 70 percent of said hydrogen atoms has been replaced with fluorine atoms and the terminal group is CHF and preferably CF
  • the perfluoroalkanamide can be prepared from the perfluoroalkanoic acid by reaction with ammonia or by any of the classical methods for producing carboxylic acid amides. For example, isobutylperfluorobutanoate,
  • perfluorooctanamide was produced from butyl perfluorooctanoate, CF (CF COOBu, and dried ammonia gas (dried with soda-lime).
  • Butylperfluorooctanoate was dissolved in ethyl ether and charged to a flask cooled in an ice-salt bath. After no more ammonia gas was absorbed by the solution of the ester, the ether was removed by distillation. (The melting point of the amide is higher than the boiling point of butanol.) After the removal of butanol the still residue was recrystallized from a mixture of toluene and anhydrous Solox in the ratio of 60 to 40 by volume.
  • Solox is said to be an alcohol base general-purpose solvent consisting of parts especially-denatured alcohol, 5 parts ethyl acetate, and 1 part aviation gasoline.
  • Anhydrous 200 grade is made from 200-proof denatured alcohol and has a specific gravity 0.7997, a distillation range of 75-80 C., and a flash point of 42 F.
  • the yield was 35 percent of theoretical.
  • the amide had a melting point of 138 C. as given in the literature.
  • benzene can be added to the reaction mixture after the removal of the ether and the crude amide precipitated, separated from the benzene-reaction mixture, washed with cold benzene and recrystallized from a Solox-benzene mixture (4 to 1 by volume). The yield in this manipulation being 55 percent of theoretical with a melting point of 142 C.
  • the butyl perfiuorooctanoate can be dissolved in benzene, the solution saturated with dry ammonia, and the amide crystallized from Solox-benzene with a yield of 32 percent of theoretical.
  • a further alternative method involves dissolving the perfluoroalkanoate in toluene, saturating the solution with dry ammonia, and recrystallizing the amide from a mixture of parts by volume of toluene to 1 part by volume of ethanol. The yield of amide in this modification is 49 percent of the theoretical.
  • the monomethylol derivative of the perfluoroalkanamide can be prepared by reacting the amide and formaldehyde in the molar proportion of 1 to an excess of 1, e.g., 1.5 mols of formaldehyde.
  • the monomethylol derivative of perfluorobutanamide was prepared.
  • the dimethylol derivative of perfluorooctanamide was prepared as follows:
  • the pH of 110 parts by weight of iropropanol was adjusted to pH 1.0 by the addition of two drops of 50 percent hydrochloric acid.
  • the perfluorooctanamide (0.1 mol) was added to the acidic isopropanol and the solution charged to a three-neck flask equipped with a stirrer, a condenser, and a thermometer. Two-tenths of a mol of paraformaldehyde was charged to the flask and the flask heated to reflux for twenty minutes to dissolve the paraformaldehyde.
  • the flask and contents were cooled to room temperature and dilute caustic soda added to adjust the pH to 10.9.
  • the alkaline reaction mixture was heated at reflux temperature for one hour when the solution was clear. When the reaction mixture is cooled to room temperature it forms a jelly. Determination of the free formaldehyde in the reaction mixture showed that 97 percent of the formaldehyde had reacted.
  • the dimethylol derivative of perfluorobutanamide was prepared in the same manner as the monomethylol derivative except that the mo] ratio of amide to paraformaldehyde was 1 to 2 rather than 1 to 1.5. Determination of the free formaldehyde in the reaction mixture showed that 95 percent of the formaldehyde had reacted.
  • the methylol derivatives of the perfluoroalkanamide of the present invention are waxy solids insoluble in water but soluble in lower aliphatic alcohols such as propanol and isopropanol, hydrocarbons such as benzene, toluene, and xylene, and ketones such as acetone. This property of being insoluble in water,
  • the methylol derivatives of the perfluoroalkanamides of the present invention are reacted with the active hydrogen of the substrate, e.g., cotton in the presence of acidic catalysts such as ammonium chloride, oxalic acid, zinc nitrate, lactic acid, and the like at a temperature in the range of about 80 to about 300 F. for a time inversely proportioned to the temperature. For example, employing lactic acid the time is twenty-four hours at room temperature. It will be observed that the catalysts are strong acids or salts of strong acids which hydrolyze to give an acid reaction. Thus, neither ammonium acetate nor sodium chloride is a catalyst for this purpose.
  • the monomethylol derivative of pentadecafluorooctanamide was affixed to cotton employing various acidic complexes to give the water, oil, and oily particulate soil repellencies indicated in the following table:
  • Oil repellent and oily particulate-soil repellent textile comprising a textile polymer having as part of the polymer molecule reactive hydrogens for which there has been chemically substituted a plurality of radicals selected from the group consisting of where Q is a perfluoroalkyl group having three to twentyone carbon atoms and at least two to fifteen fluorine atoms in said alkyl chain and the terminal group in the perfluoroalkyl chain is selected from CHF and -CF and R is a member of the group consisting of hydrogen, alkyl group having one to six carbon atoms and a cycloalkyl group having five to six carbon atoms.
  • Oil repellent and oily particulate-soil repellent textile comprising a textile polymer having as part of the polymer molecule reactive hydrogens in the surface of said polymer, said reactive hydrogens having been chemically substituted by a plurality of radicals selected from the group consisting of Q,CITI-OHZO and QCN-CH2O (I-I) R, (N) 61120-- where Q is a perfiuoroalkyl group having three to twentyone carbon atoms and at least two to fifteen fluorine atoms in said alkyl chain and the terminal group in the perfluoroalkyl chain is selected from CHF and CH and R is a member of the group consisting of hydrogen, alkyl group having one to six carbon atoms and a cycloalkyl group having fixe to six carbon atoms.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US301597A 1963-08-12 1963-08-12 Textiles reacted with methylol perfluoroalkanamides Expired - Lifetime US3322490A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US301597A US3322490A (en) 1963-08-12 1963-08-12 Textiles reacted with methylol perfluoroalkanamides
DE1469289A DE1469289C3 (de) 1963-08-12 1964-08-01 Wasser-, Öl- und schmutzabweisende Ausrüstungen auf aktive Wasserstoffatome enthaltenden Textilien
CH1024064A CH461428A (de) 1963-08-12 1964-08-05 Verfahren zum dauerhaften Wasser-, Öl- und Schmitzabweisendmachen von Textilien
FR984796A FR1534665A (fr) 1963-08-12 1964-08-11 Produit pour le traitement des textiles et procédé pour son application
GB32677/64A GB1058818A (en) 1963-08-12 1964-08-11 Methylol and alkoxymethyl derivatives of fluorinated amides and their use in treating textiles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US301597A US3322490A (en) 1963-08-12 1963-08-12 Textiles reacted with methylol perfluoroalkanamides

Publications (1)

Publication Number Publication Date
US3322490A true US3322490A (en) 1967-05-30

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US301597A Expired - Lifetime US3322490A (en) 1963-08-12 1963-08-12 Textiles reacted with methylol perfluoroalkanamides

Country Status (5)

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US (1) US3322490A (de)
CH (1) CH461428A (de)
DE (1) DE1469289C3 (de)
FR (1) FR1534665A (de)
GB (1) GB1058818A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4362527A (en) * 1982-01-04 1982-12-07 The United States Of America As Represented By The Secretary Of Agriculture Radiation-resistant fluoroaromatic cellulosic ethers
US5931970A (en) * 1995-05-12 1999-08-03 Stockhausen Gmbh & Co. Kg Process for treating leathers with surfactants to improve water repellency

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2502478A (en) * 1947-02-27 1950-04-04 American Cyanamid Co Tetrafluorosuccinic acid derivatives and their preparation
US3248260A (en) * 1961-08-22 1966-04-26 Du Pont Interpolymers of nu-methylol acrylamides and compositions containing same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2502478A (en) * 1947-02-27 1950-04-04 American Cyanamid Co Tetrafluorosuccinic acid derivatives and their preparation
US3248260A (en) * 1961-08-22 1966-04-26 Du Pont Interpolymers of nu-methylol acrylamides and compositions containing same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4362527A (en) * 1982-01-04 1982-12-07 The United States Of America As Represented By The Secretary Of Agriculture Radiation-resistant fluoroaromatic cellulosic ethers
US5931970A (en) * 1995-05-12 1999-08-03 Stockhausen Gmbh & Co. Kg Process for treating leathers with surfactants to improve water repellency

Also Published As

Publication number Publication date
GB1058818A (en) 1967-02-15
DE1469289C3 (de) 1974-12-19
DE1469289A1 (de) 1970-03-12
FR1534665A (fr) 1968-08-02
CH461428A (de) 1968-10-31
CH1024064A4 (de) 1968-05-15

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