US3392046A - Fibrous organic material having affixed thereto a polyperfluoro alkyl methacrylate ester and method for making same - Google Patents

Fibrous organic material having affixed thereto a polyperfluoro alkyl methacrylate ester and method for making same Download PDF

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Publication number
US3392046A
US3392046A US288442A US28844263A US3392046A US 3392046 A US3392046 A US 3392046A US 288442 A US288442 A US 288442A US 28844263 A US28844263 A US 28844263A US 3392046 A US3392046 A US 3392046A
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United States
Prior art keywords
water
oil
fabric
polymer
cotton
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US288442A
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English (en)
Inventor
Marder Herman Lowell
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Colgate Palmolive Co
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Colgate Palmolive Co
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Priority to US288442A priority Critical patent/US3392046A/en
Priority to DE1469285A priority patent/DE1469285C3/de
Priority to CH1669064*A priority patent/CH555313A/de
Priority to GB24995/64A priority patent/GB1045896A/en
Priority to FR978586A priority patent/FR1402216A/fr
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Publication of US3392046A publication Critical patent/US3392046A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/22—Esters containing halogen
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • 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
    • Y10T442/2164—Coating or impregnation specified as water repellent
    • Y10T442/2172—Also specified as oil repellent
    • 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
    • Y10T442/2164—Coating or impregnation specified as water repellent
    • Y10T442/2189—Fluorocarbon containing

Definitions

  • the present invention relates to the preparation of omega-fiuoroor terminal -CF polymers of methacrylic acid and to the treatment of fibrous materials such as paper, leather, textiles and the like with the aforesaid omega-fluoroor terminal -CF polymers.
  • Such products comprise generally a composition containing:
  • a paraffin wax or mixtures of vegetable wax esters such as carnauba, candililla, or sugar cane wax such as carnauba, candililla, or sugar cane wax.
  • An emulsifying agent generally glue, gelatin, and
  • thermosetting nor reaction with the fiber occurs with such products, they all ane non-durable to washing and dry-cleaning.
  • water repellency for rain wear fabrics such products produce fabrics which have a fair degree of spot and stain resistance to water-borne stains.
  • Fabrics treated with such a compound are durably water repellent, are porous, soft, and appear like untreated fabrics.
  • the stearamidomethyl analogue of Velan having a composition corresponding to the formula:
  • 017E356 ONHCH IE G is known commercially as Zelan and Norane R.
  • the advantage of the stearamide product is greater initial water repellency and greater durability to washing. Such products are still leaders in rain wear fabric finishes.
  • brous materials are made repellent to particulate soils and the residue of the aforesaid particulate soil remaining on the fibrous material after conventional laundering is markedly reduced, by aflixing to the fibrous material polymerized perfluoroalkyl esters of methacrylic acid.
  • the polyperfluoroalkyl esters of methacrylic acid have Table II is a comparison of 2 HM-8 and 3 HM-7 polymeric coatings on 80 x 80 cotton fabric obtained by padding the fabric with 1% solutions of each polymer in 1,3-bis(trifluoromethyl)benezene, followed by drying to remove the solvent.
  • the coatings exhibit the following characteristics TABLE 11 Liquid Repellency Rating Staining Characteristics Polymer Water Spray Oil Water Borne Oil Borne Repel- Launder- Repel- Launderlency ability lency ability (a) 2 HM-8 100 100/90 6. 4 8. 8 8. 9. 0
  • F fluorine and x is 1 to 20, preferably 2 to 12.
  • the monomer should be polymerized sufliciently so that it is not soft and tacky and should be substantially free from unconverted monomer and other low molecular weight telomers.
  • the inherent viscosity which is a measure of the degree of polymerization will vary depending upon the particular fluorinated ester but will be usually within the range of about 0.2 to 3, and preferably at least about 0.5, said inherent viscosity being determined by the method described in Sorenson and Campbell, Preparative Methods of Polymer Chemistry, Interscience Publishers, N.Y., 1961.
  • the invention in its broadest aspect is not limited to this range since lower and higher polymers are useful also. In general it is considered that the number of repeating units (n) will be at least about 10 which can be illustrated by enclosing the above formula in brackets followed by the subscript n.
  • novel perfiuoroalkyl esters of methacrylic acid having a terminal CF group are to be distinguished from the capabilities of either (1) methacrylic acid esters having a terminal CHF group or (2) acrylic acid esters having a terminal CF group.
  • the novel methacrylic acid esters having a terminal CF group of the present invention endow the treated substrate or fabric with a more universal resistance to soiling than is given to fabrics or substrates by either acrylic acid esters having a terminal CF group or the methacrylic acid esters having a terminal -CHF group. This is established by the data presented in the following tables using the test procedures described hereinafter involving comparisons of the properties of the polymers of the following three materials:
  • the 2 HM-8 polymer exhibits particularly unusual and effective antistaining characteristics in comparison to the effects produced by the 3 HM7 polymer (the higher the rating number approaching 10 means the greater the resistance to staining, and the higher the launderability number meaning the better removal of the stain).
  • Another unique property of the polymers of the present invention is their resistance to particulate soil.
  • fabric treated with the corresponding poly-acrylate esters exhibit elfective liquid repellency properties also, but these materials are particularly deficient in resistance to dry soil.
  • the marked superiority of the methacrylate polymers of the present invention in comparison to the acrylate types is illustrated in Table III wherein the 2 HM-S polymer is compared to the previously-described 2 I-IA-8 and to a commercial product having a polymer of a modified fluoroacrylate ester known as FC-208. For these tests, the cotton fabric is padded as described with a 2% concentration of the polymers and dried.
  • the treated materials are subjected to staining by particulate oily dirt and the reflectance of the fabric is measured before and after washing, in comparison to an untreated control.
  • a higher value indicates greater whiteness and therefore less staining of the fabric by the particulate soil.
  • the unusual properties of the fabric treated with the 2 HM-8 polymer of the present invention is self-evident from the data.
  • the 2 HM-8 polymer-treated fabric, before laundering, exhibited much greater resistance to dry soil as compared to the untreated cotton as a control.
  • the fabrics treated with the 2HA-8 and FC-208 materials exhibited no significant improvement in resistance to the particulate soil since their reflectance value before laundering were approximately the same as the untreated fabric.
  • the comparative reflectance values after laundering are particularly significant also.
  • the fabric treated with the 2 HM-8 polymer was found to be as clean as the untreated cotton.
  • the fabrics treated with the acrylate polymers were found to be far dirtier than the untreated cotton indicating incomplete removal of the adsorbed soil to a substantial degree.
  • these polymeric materials appear to promote retention of particulate soil in addition to offering no resistance to its pickup on the fabric.
  • a moments reflection recognizes that the major mechanism of soiling is the dynamic contact of a clean surface, such as the neckband or the cufi of the sleeve of a mans shirt with a surface having thereon particulate soil such as the dust and dirt held on the neckband or cuff by the oily exudations of the human skin.
  • a mans shirt treated with the other polymers indicated above will appear tattle-tale grey after washing, whereas a shirt treated with the 2 HM-8 polymer of the present invention will appear clean, white, and not tattle-tale grey.
  • novel monomeric esters of the present invention are prepared by the classical methods of organic chemistry such as the esterification of methacrylic acid with the alpha, alphadihydroperfluoroalkanol [CF (CH CH OH] with distillation of the water produced or by reaction of methacrylyl chloride with the perfluoroalkanol in the presence of an acid acceptor or by the reaction of methacrylic anhydride with the perfluoroalkanol.
  • 1,1-dihydropentadecafluorooctylmethacrylate was prepared from the following charge in the manner described hereinafter.
  • Fraction 2-2 was practically percent of the monomer, dihydropentadecafluorooctyl ester of methacrylic acid.
  • Fraction 21 was a mixture of the alcohol and the aforesaid monomer.
  • Similar methacrylate monomers are prepared in like manner from other fluorinated alcohols having a similar structure such as the corresponding 1,1 dihydro butyl, nonyl, decyl and dodecyl alcohols and the like (all other hydrogens being replaced by fluorine).
  • the monomeric methacrylic acid esters of perflu-oroalkanols having a terminal -CF group are polymerizable by known emulsion polymerization techniques employing anionic, non-ionic, and cationic surfactants.
  • the method of polymerization may be by emulsion, solution or bulk, with ionic or radical catalysts.
  • a preferred emulsion technique is exemplified by the following example:
  • the polymer emulsion is usually dried at elevated temperature to remove the unconverted monomer.
  • the 2 HM-8 polymer obtained is a hard, tough material which is non-rubbery and non-tacky at room temperature. This solid melts to form a clear viscous liquid when heated to about 550 F. Upon analysis, it corresponds to the structure:
  • the polymeric materials may be applied in any suitable manner.
  • the substrate e.g. cotton, was
  • a known weight of 80 x 80 cotton print cloth (Style #400-test fabrics) was immersed in a known quantity of water and an aqueous emulsion of the polymer slowly added to provide the test concentration of polymer in the bath for an 80 to 90 percent wet pick-up.
  • the bath was agitated for 10 minutes, the test cotton removed from the bath, and passed through the rollers once (one nip).
  • the test cotton was then dried and cured at a temperature in the range of room temperature to about 375 F.
  • these polymerized perfluoroalkyl esters of methacrylic acid having a terminal CF group also can be applied to the substrate from a solution in a solvent for the esters such as tritiuoromethyl benzene, i.e., trifiuorotoluene, hexafluoroxylene, aliphatic fluoroesters such as methylperfiuoroacetate and similar perfiuoro organic solvents.
  • tritiuoromethyl benzene i.e., trifiuorotoluene
  • hexafluoroxylene i.e., hexafluoroxylene
  • aliphatic fluoroesters such as methylperfiuoroacetate and similar perfiuoro organic solvents.
  • trifluorotoluene it is preferred to use trifluorotoluene as the solvent.
  • pentadecafiuorooctyl me-thacrylate as a 1 percent solution in his (trifluoromethyl) benzene was applied to cotton cured 10 minutes at 300 F. and subjected to the tests described herein after was found to exhibit excellent water-repellency, oil-repellency and dry stain repellency.
  • the polymer is deposited from a liquid medium such as the aqueous emulsion so that the treated fibrous material has an elemental fluorine analysis in the range of 0.05 to 5%.
  • the polymer is usually deposited on the fabric in an amount of 0.1 to by weight of the fabric.
  • the fabric treated with the polymeric materials may be dried in any suitable manner, including air-drying, i.e., room temperature of about 70- 75 F., to about 375 F. It is preferred to air-dry followed by curing, though the curing may be of the wet fabric directly, at an elevated temperature in known manner such as up to about 375 F. for about 5 to 60 minutes, preferably about 200 to 375 F.
  • a spray rating number 70/0 indicates a 70 spray rating pattern.
  • the 0 in the denominator indicates wetting to the under surface of the cloth at the wet areas but does not differentiate between small or large areas of wetting through.
  • the AATCC Standard Test Method 22-1952 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 the subsequent treatments applied. 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 a 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 degrees to the horizontal.
  • Two hundred and fifty milliliters of water at i2 F. is poured into the 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 degrees.
  • the modification is concerned with a refinement of the rating system.
  • the oil repellency rating in the numerator refers to the normal 3M rating system.
  • the number in the denominator refers to the highest rated drop not wet through as observed when turning the specimen over at the end of the specified period of three minutes. To determine fine points in ratings below 50/0, the following symbols were designated:
  • Period with no wetting Symbol or penetration 0+ 2 to 30 seconds 0+2 30 to seconds 0+3 1 90 seconds to just below 3 minutes.
  • the standard oil-heptane mixture are contained in small stoppered medicine dropper bottles. A drop of each mixture is placed on the fabric to be tested. The appearance of the test oil is observed through the drop. Note whether wetting or penetration occurs. The number corresponding to that mixture containing the highest percentage of n-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 determined better by observing the other side of the fabric. In some cases of 0 oil/heptane rating, the symbol 0+ has been used to indicate some resistance to wetting by oil.
  • Stain repellency liquid stains
  • the fabrics to be tested are stretched lightly on 12" x 31 frames. All or part of the frame area is used depending upon the amount of the test fabric available.
  • the frames are supported at both ends with the fabric about 8 inches above a black horizontal surface. The fabric touches nothing except the frame.
  • Three inch medicine droppers are used to draw the liquid stains from their containers. Each stopper is callbrated and marked on the exterior for a volume of one cubic centimeter. The liquid stain is squeezed vertically downward from a height of 2 inches above the cloth.
  • Duplicate sets of stains are applied in separate areas so that one-half of the fabric can be Washed.
  • the wash is carried out with 50 grams of Fab, a cotton cycle, and a dummy lead to total 5 pounds in a Norge Home Automatic Washer.
  • Dry soil test Fifteen to twenty 6" x 8" numbered specimens, usually 80 X 80 cotton, including at least one untreated control are tumbled for thirty minutes with 10 percent, based on the weight of the fabric of Cyanamid Soil. The tumbling is carried out in a 5 liter capacity Five Minute Home Cleaner at 44 r.p.m. Six No. 8 neoprene rubber stoppers are distributed among the specimens to increase mechanical action. At the end of the tumbling, the specimens are removed and each shaken up and down fifteen times by hand to remove surface dirt.
  • the specimens are then cut to produce two pieces each 4" x 3".
  • One half, i.e., one piece is washed with 50 grams of Fab in a cotton cycle with a five pound dummy load, then hung to dry and lightly ironed under a clean cotton cloth.
  • the degree of soil is determined with the Photovolt Reflectance Meter (Tri Blue filter). Six readings per specimen are made and the arithmetic average reported.
  • the Cyanamid Soil is prepared by blending the dry ingredients thoroughly.
  • the blended dry ingredients are dried in a forced draft convection oven for eight hours at 50 C., then milled twenty-five hours with ceramic balls and stored in a polyethylene bag.
  • the polymers are generally more heat, light and chemically stable than various fiuoro chemical sizing agents known in the art.
  • Fibrous organic material having afiixed thereto in an amount suificient to render said material resistant to water, oil, water-borne stains, oil-borne stains and dry soils, a polymer of a perfiuoroalkylmethacrylate ester having the formula where F is a fluorine and x is 1 to 20.
  • a method of making fibrous organic material repellent to particulate soil and to reduce the residue of said particulate soil remaining on said fibrous material after laundering whilst making said fibrous material resistant to water, oil, water-borne stains, oil-borne stains and dry soils which comprises depositing a polymer of perfluoromethacrylate ester on said fibrous material, said ester having the formula:
  • F fluorine and X is 1 to 20, maintaining said treated fibrous material at a temperature in the range of room temperature to about 375 F. and obtaining treated fibrous material having a fluorine content in the range of 0.05 to 5 percent.
  • a method as defined in claim 5 is deposited by padding.
  • a method of making fibrous organic material sub strate resistant to soiling by particulate soil and to reduce the residue of said particulate soil remaining on said fibrous material after laundering whilst making said fibrous material resistant to water, oil, water-borne stains, oil-borne stains and dry soils which comprises contacting said substrate, with an aqueous emulsion of polymeric perfluoroalkylmethacrylate ester, said ester having the formula:
  • the polymer where F is fluorine and X is 1 to 20 in amount to provide at least about 0.1 to about percent by weight of said poly-perfluoroalkylmethacrylate based upon the weight of said substrate, separating the so-treated substrate from said aqueous emulsion and drying said treated substrate at a temperature in the range of room temperature to about 375 F.
  • a method of making fibrous organic material re- 12 sistant to soiling by particulate soil and to reduce the residue of said particulate soil remaining on said fibrous ma terial after laundering whilst making said fibrous material resistant to water, oil, water-borne stains, oil-borne stains and dry soils which comprises contacting fibrous material hereinafter designated substrate, with a solution of a polymeric perfiuoroalkylmethacrylate ester in per fiuoro-organic solvent, said ester having the formula;
  • F fluorine and x is 1 to 20
  • separating the sotreated substrate from said perfluoro organic solvent and curing said separated substrate at a curing temperature above room temperature and not in excess of about 375 F. to remove substantially all of said perfluoro-organic solvent.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paper (AREA)
US288442A 1963-06-17 1963-06-17 Fibrous organic material having affixed thereto a polyperfluoro alkyl methacrylate ester and method for making same Expired - Lifetime US3392046A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US288442A US3392046A (en) 1963-06-17 1963-06-17 Fibrous organic material having affixed thereto a polyperfluoro alkyl methacrylate ester and method for making same
DE1469285A DE1469285C3 (de) 1963-06-17 1964-06-11 Verfahren zur wasser-, öl-,fleck- und staubabweisenden Ausrüstung von Fasermaterialien. nm: Colgate-Palmolive Co., New York, N.Y. (V.St.A.)
CH1669064*A CH555313A (de) 1963-06-17 1964-06-12 Verfahren zur herstellung eines vorpolymerisates aus fluoralkylmethacrylaten.
GB24995/64A GB1045896A (en) 1963-06-17 1964-06-16 Polymers of a fluorine-containing ester of methacrylic acid and their use for treating fibrous materials
FR978586A FR1402216A (fr) 1963-06-17 1964-06-17 Composés pour le traitement des matériaux fibreux et procédé pour leur application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US288442A US3392046A (en) 1963-06-17 1963-06-17 Fibrous organic material having affixed thereto a polyperfluoro alkyl methacrylate ester and method for making same

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US3392046A true US3392046A (en) 1968-07-09

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CH (1) CH555313A (de)
DE (1) DE1469285C3 (de)
GB (1) GB1045896A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3479214A (en) * 1964-09-21 1969-11-18 Us Agriculture Enhancing repellency of fibrous materials with fluoroalkyl acrylates
US5314959A (en) * 1991-03-06 1994-05-24 Minnesota Mining And Manufacturing Company Graft copolymers containing fluoroaliphatic groups
US5326823A (en) * 1991-03-06 1994-07-05 Minnesota Mining And Manufacturing Company Polyfluoropolyether graft copolymers
WO2009064503A1 (en) * 2007-11-12 2009-05-22 Perfect-Dry Inc. Fabric treatment process
US20100168318A1 (en) * 2007-03-21 2010-07-01 E.I. Du Pont De Nemours And Company Fluorobetaine copolymer and fire fighting foam concentrates therefrom

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2642416A (en) * 1950-05-26 1953-06-16 Minnesota Mining & Mfg Fluorinated acrylates and polymers
US3102103A (en) * 1957-08-09 1963-08-27 Minnesota Mining & Mfg Perfluoroalkyl acrylate polymers and process of producing a latex thereof
US3282905A (en) * 1961-05-03 1966-11-01 Du Pont Fluorine containing esters and polymers thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2642416A (en) * 1950-05-26 1953-06-16 Minnesota Mining & Mfg Fluorinated acrylates and polymers
US3102103A (en) * 1957-08-09 1963-08-27 Minnesota Mining & Mfg Perfluoroalkyl acrylate polymers and process of producing a latex thereof
US3282905A (en) * 1961-05-03 1966-11-01 Du Pont Fluorine containing esters and polymers thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3479214A (en) * 1964-09-21 1969-11-18 Us Agriculture Enhancing repellency of fibrous materials with fluoroalkyl acrylates
US5314959A (en) * 1991-03-06 1994-05-24 Minnesota Mining And Manufacturing Company Graft copolymers containing fluoroaliphatic groups
US5326823A (en) * 1991-03-06 1994-07-05 Minnesota Mining And Manufacturing Company Polyfluoropolyether graft copolymers
US5336717A (en) * 1991-03-06 1994-08-09 Minnesota Mining And Manufacturing Company Graft copolymers containing fluoroaliphatic groups
US20100168318A1 (en) * 2007-03-21 2010-07-01 E.I. Du Pont De Nemours And Company Fluorobetaine copolymer and fire fighting foam concentrates therefrom
US8916058B2 (en) 2007-03-21 2014-12-23 E I Du Pont De Nemours And Company Fluorobetaine copolymer and fire fighting foam concentrates therefrom
WO2009064503A1 (en) * 2007-11-12 2009-05-22 Perfect-Dry Inc. Fabric treatment process
US20090233507A1 (en) * 2007-11-12 2009-09-17 Gross Alexander L Fabric treatment process

Also Published As

Publication number Publication date
CH555313A (de) 1974-10-31
DE1469285C3 (de) 1974-12-19
DE1469285A1 (de) 1969-04-30
GB1045896A (en) 1966-10-19

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