EP0068040B1 - Polyfluoralkylester, ihre Herstellung und Verwendung - Google Patents

Polyfluoralkylester, ihre Herstellung und Verwendung Download PDF

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Publication number
EP0068040B1
EP0068040B1 EP81105066A EP81105066A EP0068040B1 EP 0068040 B1 EP0068040 B1 EP 0068040B1 EP 81105066 A EP81105066 A EP 81105066A EP 81105066 A EP81105066 A EP 81105066A EP 0068040 B1 EP0068040 B1 EP 0068040B1
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EP
European Patent Office
Prior art keywords
carbons
compound
substrate
water
cycloalkyl
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Expired
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EP81105066A
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English (en)
French (fr)
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EP0068040A1 (de
Inventor
Stanley Earl Krahler
William Roscoe Remington
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to DK284581A priority Critical patent/DK162979C/da
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to EP81105066A priority patent/EP0068040B1/de
Priority to DE8181105066T priority patent/DE3171807D1/de
Priority to JP56106323A priority patent/JPS5810539A/ja
Priority to CA000381681A priority patent/CA1233185A/en
Priority to US06/410,516 priority patent/US4517376A/en
Publication of EP0068040A1 publication Critical patent/EP0068040A1/de
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Publication of EP0068040B1 publication Critical patent/EP0068040B1/de
Expired 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
    • 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
    • D06M13/10—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 oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/236—Esters of carboxylic acids; Esters of carbonic acid containing halogen atoms
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof

Definitions

  • This invention relates to chloromethyl-substituted polyfluoroalkyl esters of polybasic acids and their use in treating a variety of substrates, such as textile fabrics and paper, so as to provide the substrate with soil resistance as well as water and oil repellancy. It relates further to a process for preparing the compounds of this invention wherein iodine-substituted polyfluoroalkyl esters are reacted with elemental chlorine in which the iodine-substituted esters are in the molten state or dissolved or suspended in an inert liquid.
  • U.S. Patent 3,716,401 discloses and claims a process for rendering a vinyl surface oil resistant by applying thereto a polymeric composition containing a vinyl polymer dissolved in a volatile solvent and an ester derived from perfluoroethanol and a mono- or poly-carboxylic acid.
  • U.S. Patent 4,034,022 discloses isomers having the formula: wherein C n F 2n+1 is a perfluorinated aliphatic chain, n is an integer from 2 to 18, X and Y are the same or different and are each a halogen atom, a hydoxyl radical, the group OM in which M is a metallic equivalent or an alkoxy, chloroalkoxy, hydroxypolyalkyleneoxy, aryloxy or -NZZ' group in which Z and Z' are the same or different and are each a hydrogen atom or an alkyl, cycloalkyl or aryl group.
  • the compounds are liable to find use as emulsifying or foaming agents, particularly when a tensioactive agent resistant to acids and oxidants is needed, as leveling or anti-stain agents for polishes or emulsion paints, as corrosion inhibitors, solvent evaporation retarders or as hydrophobic and oleophobic agents.
  • This invention relates to compounds having the formula: wherein
  • R f is a saturated, monovalent, non-aromatic, aliphatic radical.
  • the chain may be straight, branched or cyclic, and may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms bonded only to carbon atoms.
  • a fully fluorinated group is preferred, but hydrogen or chlorine atoms may be present as substituents in the fluorinated aliphatic radical provided that not more than one atom of either is present in the radical for every two carbon atoms, and that the radical must at least contain a terminal perfluoromethyl group.
  • the fluorinated aliphatic radical contains not more than 20 carbon atoms because such a large radical results in inefficient use of the fluorine content.
  • R f is a perfluoroalkyl containing 3 to 20 carbons.
  • the compounds of this invention can be prepared by the reaction set forth in the following equation:
  • iodine substituted polyfluoroalkyl ester starting material for the preparation of the compounds of this invention can be prepared by the reaction set forth in the following equation:
  • R 1 is alkyl, aryl, aralkyl or cycloalkyl.
  • R 1 can be the residue remaining after esterification of citric, phthalic (o, m or p isomer), benzoic, succinic, chlorendic, benzene polycarboxylic acids, such as trimellitic, pyromellitic and the like.
  • the reaction of the iodine-substituted polyfluoroalkyl ester with chlorine can be carried out by melting the iodine-substituted polyfluoroalkyl ester and contacting the molten ester with chlorine, or the iodine-substituted polyfluoroalkyl ester can be suspended or dissolved in a suitable liquid and reacted with chlorine.
  • a suitable liquid is inert under the reaction conditions; e.g. alcohols or water should be avoided since they would be expected to react.
  • Preferred liquids include 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,1,2-tratrachloro-2,2-difluoroethane and tetrachloromethane.
  • chloroform All such halocarbons function as solvents for the iodine substituted polyfluoroalkyl ester starting material.
  • the liquid medium be a solvent for that ester, it is preferred that the ester be at least partially soluble in the liquid medium.
  • the reaction of the iodine-substituted polyfluoroalkyl ester with chlorine is mildly exothermic, being somewhat more exothermic at the start of the reaction than at a point near its completion.
  • reflux thereof provides effective control of the exotherm.
  • the temperature of the reaction with chlorine is not critical nor is pressure.
  • the reaction is run at a temperature between about 40° and 55°C when a solvent is used, and between about 85° and 90° when the ester starting material is molten during the reaction with chlorine.
  • the reaction whether in solution or in molten form, is usually run at atmospheric pressure, elevated pressures can be used as well. Normally, the reaction is run until essentially all of the covalently bound iodine is displaced from the ester.
  • the preparation of the iodine-substituted polyfluoroalkyl ester is carried out in the presence of a free radical initiator at temperatures in the range between about 50° and 140°C and at pressures between about 1 and 50 atmospheres. If the polyfluoroalkyl iodide orthe allyl ester used in the reaction has a boiling point below the desired reaction temperature, a pressure system would be used; otherwise, the reaction may be carried out at atmospheric pressure.
  • the free radical initiator may be either an azo compound or a peroxy compound, e.g.
  • the polyfluoroalkyl iodides can be prepared by a variety of reactions. See for example Brace et al., JACS, 73, 4016 (1951); Krespan, J. Org. Chem., 23, 2016 (1958); Haszeldine, J. Chem. Soc., 1949, 2856; 1952, 4259; 1953, 376; Hauptschein et al., JACS, 79, 2549 (1957).
  • the principal use of compounds of this invention involves application of solutions or aqueous dispersions of said compounds to carpets, other woven or non-woven textiles, or paper.
  • the desirable characteristics imparted by the application of said compounds include water repellency, oil repellency, and resistance to soiling. The degree to which said desirable characteristics are acheived is evaluated in different ways for the different substrates.
  • dry soil resistance provides a measure of the ability of the carpet to retain its new appearance under normal traffic conditions.
  • oil and water repellency is required in carpets to provide resistance to staining by spilled liquids.
  • aqueous dispersions of compounds of this invention can be blended with an aqueous polymeric suspension.
  • aqueous suspension of polymethyl methacrylate makes a composition which can be diluted with water for application to the various substrates contemplated by this invention.
  • the presence of the polymeric suspension improves dry soil resistance.
  • a dispersion before dilution with water, will normally contain from about 2% to about 20% of fluorinated ester of this invention and between about 2% and about 40% of the polymer, dry basis, provided by the above-mentioned suspension.
  • the above-described dispersion is diluted still further with water.
  • Application can be made by any known technique, such as padding, exhaust spraying, and the like.
  • a compound (or compounds) of this invention as a solution or dispersion and optionally containing other components such as, for example, poly(methylmethacrylate), has been applied to the desired substrate, it will usually be dried to remove water and/or solvent. Normally, drying is effected by heating to about 120-170°C, although higher or lower temperatures may be used. In particular, drying at ambient temperature is frequently sufficient, although heating is usually preferred to hasten the drying. Furthermore, repellency effects frequently are improved by heat treatment beyond that required for drying. It appears that such treatment at least partially melts the composition of this invention so that it spreads and more effectively coats the substrate.
  • Oil repellency test used herein is an adaptation of AATCC Test Method 118-1978.
  • Oil repellency is defined as the ability of a substrate to resist wetting by oily liquids.
  • drops of standard test liquids consisting of a selected series of hydrocarbons with varying surface tensions, are placed on the substrate and observed for wetting.
  • the oil repellency rating is the highest numbered test liquid which will not wet the surface of the substrate within a period of 30 seconds. Wetting of the surface of the substrate is normally evident by a darkening thereof at the interface. On black or dark surfaces wetting can be detected by a loss of "sparkle" within the drop.
  • the standard test liquids are set forth in Table 1. "Nujol” is the trademark of Plough, Inc., for a mineral oil having a Saybolt viscosity of 360/390 at 100°F (38°C) and a specific gravity of 0.880/0.900 at 60°F (15°C).
  • the water repellency test provides an index of aqueous stain resistance in that, generally, the higher the water repellency rating, the better the resistance to staining by water-based substances. Like the oil repellency rating, the water repellency rating is the highest numbered test liquid which will not wet the surface of the substrate in a specified amount of time, in this case 10 seconds.
  • the standard test solutions are those of Table 2.
  • test liquid Water Repellency Rating No. 1
  • drops of the next higher numbered test liquid are placed in an adjecent site and observed for 10 seconds.
  • the above-described procedure is continued until at least two or the three drops of the test liquid fail to remain spherical or hemi-spherical 10 seconds after application.
  • mixed perfluoroalkyl iodides be used in making compounds of this invention.
  • the term ABI is an abbreviation for 2,2'-azobis-(isobutyronitrile).
  • deoxygenated means that the material so treated was stirred overnight at ambient temperature under a current of nitrogen or stirred for at least one hour at about 60°C under a current of nitrogen.
  • nonionic surfactant means the product of the reaction of 15 moles of ethylene oxide with 1 mole of a mixture of n-dodecanol-1, n-tetradecanol-1, and n-hexadecanol-1.
  • “Arquad” 18-50 means a 50% solution of octadecyl trimethyl ammonium chloride in water.
  • the MPI and the triallyl trimellitate were mixed and deoxygenated. Then, while maintaining a nitrogen atmosphere, the ABI was added portionwise over a period of about 24 hours on the following time schedule:
  • a portion of the finished dispersion was diluted with water and mixed with acetic acid and an aqueous dispersion of polymethylmethacrylate (PMMA).
  • PMMA polymethylmethacrylate
  • the PMMA in the dispersion had an inherent viscosity of about 0.7 (0.5 g of PMMA in 100 ml of acetone at 30°C), and was made up of particles having an average size of about 0.06 micron.
  • the mixed dispersion comprising the adduct, acetic acid, PMMA and water was then sprayed onto the face of nylon carpet so that the face fibers of the carpet received 0.055% of fluorine (in covalently bound form), 0.186% of polymethylmethacrylate, 0.01 % of acetic acid, and about 25% of H 2 0 based on the weight of the fiber.
  • the carpet was dried for 30 minutes in a forced air oven at 270°F. Samples of the carpet were tested for oil and water repellency. Samples thereof were also tested for dry soil resistance by being placed in a heavily-travelled hallway along with untreated samples of the same carpet, being rated for soil-resistance in comparison with the untreated carpet. The results of testing of the carpet samples are set forth in Table 3.
  • Dispersions of the product of this example, with and without polymethyl methacrylate, were prepared by the procedures described in Example 1. Separate portions thereof were applied to carpet samples and tested as in Example 1, the results thereof being recited in Tables 3 and 4.
  • the organic layer was washed with 200 ml of water at 80°C, and the product in methyl isobutyl ketone formed the bottom layer.
  • the upper layer was discarded, and after evaporation of part of the methyl isobutyl ketone in the bottom layer, 339 g of residue were obtained.
  • a sample thereof was dried in a vacuum oven and found to be 67.5% non-volatile. That corresponds to 229 g of dry product which is 83% of the theoretical yield.
  • n is the same as given in the definition of MPI.
  • the structure of the product was established by NMR spectroscopy and is supported by elemental analysis. The latter gives the following results for n with an average value of 8: Preparation of Dispersion and Testing on Carpet
  • Example 1 A dispersion was prepared as described in Example 1, using 352 g of the 67.5% solids methyl isobutyl ketone solution described above. The other ingredients were: Homogenization, removal of methyl isobutyl ketone, application to carpet (with and without polymethyl methacrylate) and testing were carried out as described in Example 1. Test results are set forth in Tables 3 and 4.
  • the dispersion was made as described in Example 1, using 179 g of the methyl isobutyl ketone solution produced as described above. The other ingredients were as described in Example 1, except that no methyl isobutyl ketone was added per se. The dispersion was distilled under vacuum to remove the methyl isobutyl ketone and applied to nylon carpet as hereinbefore described. The results of testing of the treated carpet are set forth in Tables 3 and 4.
  • the MPI and the diallylphthalate were mixed and deoxygenated. Then, while maintaining a nitrogen atmosphere, the ABI was added and temperature was controlled according to the following schedule:
  • Example 4 The equipment was the same as used in Example 4. The materials charged were: Chlorine gas (15 g) was introduced during two hours, while the flask contents were maintained between 39° and 55°. Thereafter, 20 ml of water were added, followed by 80 ml of a saturated aqueous solution of sodium bisulfite. The mixture separated into 2 layers and was let stand for 25 days.
  • the layers were separated, the the lower layer was washed with three 200-ml portions of water, to the last of which was added 10 ml of isopropanol.
  • the chlorofluorocarbon was then evaporated in a vacuum oven at 90-100°.
  • the product was a clear, amber, viscous liquid and weighed 102 g, representing a 94% yield of:
  • the product crystallized within a day.
  • the structure was established by elemental analysis and NMR spectroscopy, both proton and Carbon-13. The elemental analysis gave the following results:
  • the resulting mixture was transferred to a separatory funnel and 50 ml of methyl isobutyl ketone were added. After shaking, the lower layer was discarded and 50 ml of a saturated aqueous solution of magnesium sulfate and 20 ml of isopropanol were added and the mixture was shaken again. The lower layer was again discarded and 50 ml of hot water were added. After shaking, the solution of the product (lower layer) was drawn off.
  • the product solution was evaporated in vacuum (removing methyl isobutyl ketone) until it weighed 69 grams. Fifty-seven grams of the resulting product were mixed with: The resulting mixture was well agitated in a blender, then diluted with water and mixed with acetic acid. That mixture was sprayed onto nylon carpet so that the face fibers received 0.055% of fluorine (in covalently bound form), 0.01 % of acetic acid, and 25% of water based on the weight of the fiber. The carpet was dried and tested as described in Example 1. The test data are set forth in Table 4.
  • the diluted dispersions tested on non-woven fabric were:
  • the non-woven fabric was a 60% polyester/40% wood pulp fabric intended for use in operating-room garments.
  • the diluted dispersions were padded onto the non-woven fabric to obtain a wet pick-up of 193 ⁇ 5%. They were then dried by passing twice through a mangle heated to 325°F, the heat being applied once on each side of the fabric, with a contact time in the mangle of 75 seconds.
  • a one-quart mason jar is charged with 600 ml of water containing 0.9% NaCI; the disc is clamped to the top of the jar and the jar is inverted.
  • the time for water to penetrate the disc is recorded as set forth in Table 5.
  • the treating dispersions used were the same type as described in "Tests on Non-woven,” but of different concentration.
  • the paper Claremont unbleached Kraft weighing 20 Ibs/100 sq ft, was padded with the dispersions as listed to give 138 ⁇ 2% wet pick-up.
  • the paper was then dried by two passes through a 220°F mangle, once with each side up. Contact time was 75 seconds.
  • the treated papers and an untreated control were given the AATCC oil repellency test, and the results are given in Table 6.
  • Example 1 The product of Example 1 (984 g) was charged to a 3-liter round-bottom flask with bottom outlet, furnished with a heating mantle and a cold-finger for tap-water cooling. Nitrogen was passed through the flask while the contents were heated to 85°C to melt. The contents of the flask were agitated while chlorine gas was introduced below the surface of the liquid as detailed below. Agitation was stopped and the mixture was allowed to cool to room temperature and stand overnight. The following morning, the mixture was heated to 70°C and the upper, aqueous layer was siphoned off. Water (400 ml) and 490 ml of methyl isobutyl ketone were added, and the mixture was heated with agitation from 55 to 68°C.
  • Example 2 A one-liter round-bottom flask with bottom outlet was used. A mantle (Glass-Col) was used for heating. The product of Example 2 was charged to the flask at room temperature and was melted under nitrogen. Then, the contents of the flask were agitated while chlorine gas was introduced below the liquid surface, according to the following schedule: Agitation was stopped at this point and the upper, aqueous layer was siphoned off. Then, 300 ml. water were added and the mixture was reheated to 88°C with agitation. Agitation was stopped and the molten product (330 g) was drained off the bottom. A sample of the product was dried at 100°C in a vacuum oven and showed 95% non-volatiles. That represents 91 % of the theoretical yield. Elemental analysis gave the following results:

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paper (AREA)

Claims (21)

1. Verbindung der Formel
Figure imgb0045
worin
Rf ein gesättigter, einwertiger, nicht-aromatischer, fluorierter, geradkettiger oder verzweigtkettiger oder cyclischer, aliphatischer Rest ist, der durch zweiwertige Sauerstoffatome oder dreiwertige Stickstoffatome unterbrochen sein kann, die nur an Kohlenstoffatome gebunden sind, und mindestens 3 Kohlenstoffatome enthält;
R1 Alkyl, Aryl, Aralkyl, Cycloalkyl oder Cycloalkenyl; und
n eine Zahl von 1 bis 4 ist.
2. Verbindung von Anspruch 1, worin Rf ein C3―C20-Perfluoralkyl, R1 Alkyl, Aryl, Aralkyl oder Cycloalkyl und n 2 bis 4 ist.
3. Verbindung von Anspruch 1, worin Wasserstoff- oder Chloratome als Substituenten in dem fluorierten aliphatischen Rest Rf anwesend sein können, vorausgesetzt, dass nicht mehr als ein Atom jedes der beiden für je zwei Kohlenstoffatome im Rest anwesend sind und dass der Rest mindestens eine endständige Perfluormethylgruppe enthält.
4. Verbindung von Anspruch 2, worin R1 von Zitronensäure, o-, m- oder p-Phthalsäure, Bernsteinsäure, Hexachlor-endomethylentetrahydrophthalsäure oder einer Benzolpolycarbonsäure abgeleitet ist.
5. Verbindung von einem der Ansprüche 1 bis 4, worin Rf 4 bis 16 C-Atome enthält.
6. Verbindung nach Anspruch 4, worin Rf einen Durchschnittswert von 6 bis 8 C-Atomen hat.
7. Verfahren, bei dem Chlor mit einem Reaktanten von der Formel:
Figure imgb0046
umgesetzt wird, um ein Endprodukt von der Formel:
Figure imgb0047
zu erhalten, worin
Rf ein gesättigter, einwertiger, nicht-aromatischer, fluorierter, geradkettiger oder verzweigtkettiger oder cyclischer, aliphatischer Rest ist, der mindestens 3 Kohlenstoffatome enthält;
R1 Alkyl, Aryl, Alkenyl, Aralkyl, Cycloalkyl oder Cycloalkenyl; und
n eine Zahl von 1 bis 4 ist;

wobei die reagierende Verbindung während der Reaktion in geschmolzener Form oder in einem unter den Reaktionsbedingungen inerten flüssigen Medium gelöst oder suspendiert ist.
8. Verfahren nach Anspruch 7, worin Rf Perfluoralkyl mit 3 bis 20 C-Atomen und R1 Alkyl, Aryl, Aralkyl oder Cycloalkyl und n 2 bis 4 ist.
9. Verfahren nach Anspruch 8, worin Rf Perfluoralkyl mit 3 bis 20 C-Atomen ist, R1 von Zitronensäure, o-, m- oder p-Phthalsäure, Bernsteinsäure, Hexachlor-endomethylentetrahydrophthalsäure oder einer Benzolpercarbonsäure abgeleitet und n 2 bis 4 ist.
10. Verfahren nach einem der Ansprüche 7 bis 9, worin Rf 4 bis 16 C-Atome enthält.
11. Verfahren nach Anspruch 10, worin Rf einen Durchschnittswert von 6 bis 8 C-Atomen hat.
12. Verfahren, um ein Substrat öl- oder wasserabweisend oder gegen Anschmutzung von trockenem Schutz widerstandsfähig zu machen, indem man auf das substrat mindestens eine Verbindung von Anspruch 1 aufbringt.
13. Verfahren von Anspruch 12, worin Rf Perfluoralkyl mit 3 bis 20 C-Atomen, R' Alkyl, Aryl, Aralkyl oder Cycloalkyl und n 2 bis 4 ist.
14. Verfahren von Anspruch 13, worin R1 von Zitronensäure, o-, m- oder p-Phthalsäure, Bernsteinsäure, Hexachlor-endomethylentetrahydrophthalsäure oder einer Benzolpolycarbonsäure abgeleitet ist.
15. Verfahren nach einem der Ansprüche 12 bis 14, worin R, 4 bis 16 C-Atome enthält.
16. Verfahren nach Anspruch 14, worin Rf einen Durchschnittswert von 6 bis 8 C-Atomen hat.
17. Substrat, auf dem mindestens eine Verbindung von Anspruch 1 aufgebracht ist, das öl- oder wasserabweisend oder gegen Anschmutzung von trockenem Schutz widerstandsfähig ist.
18. Substrat von Anspruch 17, worin Rf Perfluoralkyl mit 3 bis 20 C-Atomen, R' Alkyl, Aryl, Aralkyl oder Cycloalkyl und n 2 bis 4 ist.
19. Substrat von Anspruch 18, worin R' von Zitronensäure, o-, m- oder p-Phthalsäure, Bernsteinsäure, Hexachlor-endomethylentetrahydrophthalsäure oder einer Benzolpolycarbonsäure abgeleitet ist.
20. Substrat nach einem der Ansprüche 17 bis 19, worin Rf 4 bis 16 C-Atome enthält.
21. Substrat von Anspruch 14, worin Rf einen Durchschnittswert von 6 bis 8 C-Atomen hat.
EP81105066A 1981-06-26 1981-06-30 Polyfluoralkylester, ihre Herstellung und Verwendung Expired EP0068040B1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DK284581A DK162979C (da) 1981-06-26 1981-06-26 Polyfluoralkylestere, deres fremstilling og anvendelse
EP81105066A EP0068040B1 (de) 1981-06-26 1981-06-30 Polyfluoralkylester, ihre Herstellung und Verwendung
DE8181105066T DE3171807D1 (en) 1981-06-30 1981-06-30 Polyfluoroalkyl esters and their preparation and use
JP56106323A JPS5810539A (ja) 1981-06-26 1981-07-09 ポリフルオロアルキル・エステルの製造方法
CA000381681A CA1233185A (en) 1981-06-26 1981-07-14 Polyfluoroalkyl esters and their use
US06/410,516 US4517376A (en) 1981-06-26 1982-08-23 Manufacture of chloromethyl-substituted polyfluoroalkyl esters

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DK284581A DK162979C (da) 1981-06-26 1981-06-26 Polyfluoralkylestere, deres fremstilling og anvendelse
EP81105066A EP0068040B1 (de) 1981-06-26 1981-06-30 Polyfluoralkylester, ihre Herstellung und Verwendung
US33861782A 1982-01-11 1982-01-11

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EP0068040A1 EP0068040A1 (de) 1983-01-05
EP0068040B1 true EP0068040B1 (de) 1985-08-14

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Publication number Priority date Publication date Assignee Title
ATE80314T1 (de) * 1987-07-14 1992-09-15 Sankyo Co Zusammensetzung zur herstellung von antithrombotischen medizinischen erzeugnissen.
GB9414570D0 (en) * 1994-07-19 1994-09-07 Secr Defence Oil and water repellent dyestuffs
US5859126A (en) * 1995-09-18 1999-01-12 E. I. Du Pont De Nemours And Company Coatings containing fluorinated esters
US5670573A (en) * 1996-08-07 1997-09-23 E. I. Du Pont De Nemours And Company Coatings containing fluorinated esters
US11142657B2 (en) 2016-03-03 2021-10-12 The Chemours Company Fc, Llc Partially fluorinated ester compound additives for architectural coatings

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US3811933A (en) * 1969-12-15 1974-05-21 Air Prod & Chem Oil and grease resistant paper products and process for treating cellulosic materials
US3752847A (en) * 1971-09-23 1973-08-14 J Fletcher Fluorinated esters of polycarboxylic acids
DE2628047A1 (de) * 1975-06-30 1977-01-27 Allied Chem Schmutzabstossende mittel und verfahren zu deren herstellung

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DK284581A (da) 1982-12-27
CA1233185A (en) 1988-02-23
JPH0451543B2 (de) 1992-08-19
DK162979C (da) 1992-06-01
DK162979B (da) 1992-01-06
EP0068040A1 (de) 1983-01-05
JPS5810539A (ja) 1983-01-21

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