DE1254150B - Process for the preparation of fluoroalkylphosphonic acid glycidyl esters - Google Patents

Process for the preparation of fluoroalkylphosphonic acid glycidyl esters

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Publication number
DE1254150B
DE1254150B DEB83727A DEB0083727A DE1254150B DE 1254150 B DE1254150 B DE 1254150B DE B83727 A DEB83727 A DE B83727A DE B0083727 A DEB0083727 A DE B0083727A DE 1254150 B DE1254150 B DE 1254150B
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glycidyl esters
acid glycidyl
preparation
minutes
calculated
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German (de)
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Walter Bloechl
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
    • 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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

Verfahren zur Herstellung von Fluoralkylphosphonsäureglyzidylestern Die Erfindung betrifft die Herstellung von Perfluoralkylglyzidylestern. Diese sind hervorragende Imprägniermittel für Textilien, Leder oder Papier, Lack oder Holz. Insbesondere die Imprägnierung von Textilien zur Erzeugung öl- und wasserabweisender Eigenschaften besitzt größere Bedeutung als schmutzabweisende Ausrüstung. Die bisher im Handel befindlichen Imprägnierungen sind jedoch nur ungenügend waschecht. Sie erfordern komplizierte Zusätze, um ihre Waschechtheit noch einigermaßen zu steigern und auch um die sonst mangelhafte Wasserabweisung zu verbessern.Process for the preparation of fluoroalkylphosphonic acid glycidyl esters The invention relates to the preparation of perfluoroalkyl glycidyl esters. These are excellent impregnating agent for textiles, leather or paper, lacquer or wood. In particular, the impregnation of textiles to make them oil and water repellent Properties is more important than dirt-repellent finish. The so far However, the impregnations available on the market are insufficiently washfast. she require complicated additives in order to increase their washfastness to some extent and also to improve the otherwise inadequate water repellency.

Mit den erfindungsgemäß hergestellten Fluoralkylphosphonsäureglyzidylestern lassen sich jedoch Textilien mit Suspensionen oder Lösungen in Wasser oder organischen Lösungsmitteln so imprägnieren, daß eine hohe oleophobe und hydrophobe Wirkung bei weitgehender Waschechtheit ohne notwendigen Zusatz anderer Hilfsmittel erzielt werden kann. Zugleich erhalten die Stoffe ein flammwidriges Verhalten. With the fluoroalkylphosphonic acid glycidyl esters prepared according to the invention However, textiles with suspensions or solutions in water or organic can be used Impregnate solvents so that they have a high oleophobic and hydrophobic effect extensive washfastness can be achieved without the need to add other aids can. At the same time, the fabrics have a flame-retardant behavior.

Erfindungsgemäß werden solche Fluoralkylphosphonsäureglyzidylester dadurch hergestellt, daß man in an sich bekannter Weise Perfluoralkylphosphonsäuren der allgemeinen Formel: Ri (CX2)nP(O)(OIl)2 in der Rf einen Perfluoralkylrest mit 8 bis 20 Kohlenstoffatomen, X Wasserstoff oder einen Alkylrest und n 2 oder 3 bedeutet, mit der doppeltmolaren Menge Epichlorhydrin in möglichst wasserfreiem Medium umsetzt und die Chlorhydrinpropylester mit Alkali oder Aminen reagieren läßt. Die Glyzidylester lassen sich besonders gut in Form von Lösungen in Trichloräthylen auf die Substrate bringen. Durch kurzfristiges Erhitzen auf 120"C kann die Härtung am Substrat vorgenommen werden. Die Fluoralkylphosphonsäuren für die erfindungsgemäße Umsetzung können gemäß der niederländischen Patentanmeldung 6 509 545 (a CO7f) vom 1. 2. 1966 (Chemical Abstracts, Vol. 64, 1966, Spalte 196 80h) durch thermische Addition von Jodperfluoralkanen an Vinylphosphonsäuredichlorid beispielsweise bei 350 C, 1 atm und 50 Sekunden Verweilzeit und anschließender Verseifung des Säurechlorids mit darauffolgender reduktiver Dejodierung mit Natriumamalgam in wäßrig-alkoholischer Lösung als Natriumsalz gewonnen werden. Aus der wäßrigen Natriumsalzlösung lassen sich darauf die freien Säuren durch Zusatz von Schwefelsäure ausfällen, abscheiden und über konzentrierter Schwefelsäure trocknen. According to the invention, such glycidyl fluoroalkylphosphonic acid esters are used produced by adding perfluoroalkylphosphonic acids in a manner known per se of the general formula: Ri (CX2) nP (O) (OIl) 2 in the Rf with a perfluoroalkyl radical 8 to 20 carbon atoms, X is hydrogen or an alkyl radical and n is 2 or 3, with twice the molar amount of epichlorohydrin in a medium that is as anhydrous as possible and reacting the chlorohydrin propyl ester with alkali or amines. The glycidyl esters can be applied particularly well to the substrates in the form of solutions in trichlorethylene bring. The substrate can be hardened by briefly heating it to 120 "C will. The fluoroalkylphosphonic acids for the reaction according to the invention can according to Dutch patent application 6 509 545 (a CO7f) of February 1, 1966 (Chemical Abstracts, Vol. 64, 1966, column 196 80h) by thermal addition of iodoperfluoroalkanes of vinylphosphonic acid dichloride, for example at 350 C, 1 atm and 50 seconds residence time and subsequent saponification of the acid chloride with subsequent reductive deiodination can be obtained as the sodium salt with sodium amalgam in an aqueous-alcoholic solution. The free acids can then be added to the aqueous sodium salt solution precipitate of sulfuric acid, separate and dry over concentrated sulfuric acid.

Es wurden Ölabweisungswerte gemäß nachstehender Tabelle erhalten. Im Vergleich dazu wurden darin auch die Werte für Fluorcarbonharzemulsionen in Wasser aufgeführt, deren Zusammensetzung den derzeit üblichen Imprägnierungen entsprach. Die angegebenen Ölabweisungswerte wurden mit Paraffinöl-n-Heptan-Lösungen getestet. Aus Testlösungen mit dem höchsten n-Heptangehalt, die gerade noch nicht benetzten, wurde der Ölabweisungswert nach der Formel: Volumprozent n-Heptan + 50 = Ölabweisungswert bestimmt. Als Testgewebe diente, sofern nicht anders vermerkt, ein extrahiertes, gewaschenes Baumwollgabardinestück, mit einem Gewicht von 265 im2. Oil repellency values were obtained in accordance with the table below. In comparison, the values for fluorocarbon resin emulsions in water were also included listed, the composition of which corresponded to the currently customary impregnations. The specified oil repellency values were tested with paraffin oil-n-heptane solutions. From test solutions with the highest n-heptane content that just barely wetted the oil repellency value according to the formula: volume percent n-heptane + 50 = oil repellency value certainly. Unless otherwise stated, an extracted, washed cotton gabardine piece, weighing 265 im2.

Nach der Tränkung des Testgewebes wurde auf eine Naßgewichtszunahme von 700/o abgequetscht und bei 1000C getrocknet. Vor der Prüfung wurden die behandelten Proben mit Wasser ausgewaschen und getrocknet. Die 3malige Waschbehandlung wurde in einer Haushaltswaschmaschine mit Feinwaschmittel vorgenommen. Probe | Gehalt des Bades Härtetemperatur Ölabweisung 3mal Nr. | Imprägniermittel | Härtezeit | | Feinwäsche 1 lO/o 1500C C2H4C12F25 P(O) JOCH, CH0 Cd2)2 2 Minuten 120 1 105 Probe Gehalt des Bades Härtetemperatur Ölabweisung 3mal Nr. Imprägniermittel Härtezeit , Feinwäsche 2 0,2 0/, 1500C C2H4C12F25 P(O) (OCH2. CH CH1 5 Minuten 110 90 o I 3 0,3°/0 1600C C2H4CllF23 P(O) (OCH2. CH0- CH2)2 2 Minuten 120 1 105 0 In 4 0,25 0/, 1600C C2H4CllF23 P(O) (OCH2. CH - CH2)2 2 Minuten 110 t 90 o /2 5 0s5°/o 1500C C2H4CloF2l P(O)(OCH2 CH - CH2)2 4 Minuten 120 1 95 o /2 6 0,5ovo 1400 C C2H4CF19 P(O) {NOCH2 CM0- CM2)2 10 Minuten 120 , 100 o 12 7 1O/o 100"C C2H4C8F17 P(O) (OCH2. CH - Cd2)2 5 Minuten 100 90 o 12 8 0,80/0 145"C C2M4C7F15 P(O) {NOCH2 CH - CH2 3 Minuten 110 90 zog 9 10/o Emulsion eines Polymerisats von 125"C CH2 - N(CH3SO, C8F17 10 Minuten 90 60 CH2-OCO CH = CH2 (Vergleich) 10 1°/o Emulsion eines Polymerisats von 150"C CH2 N(C3H7)S02 C8F17 4 Minuten 90 60 CH2-OCO CH = CH2 (Vergleich) Probe 3: Das Bad enthielt zusätzlich noch 0,10/, Zn(BF4)2.After the test fabric had been soaked, it was squeezed to a wet weight increase of 700 / o and dried at 1000.degree. Before the test, the treated samples were washed out with water and dried. The washing treatment three times was carried out in a household washing machine with mild detergent. Sample | Content of the bath. Hardening temperature. Oil repellency 3 times No. | Impregnation agent | Hardening time | | Delicates 1 10 / o 1500C C2H4C12F25 P (O) JOCH, CH0 Cd2) 2 2 minutes 120 1 105 Sample content of the bath Hardening temperature Oil repellency 3 times No. Impregnation agent hardening time, delicate wash 2 0.2 0 /, 1500C C2H4C12F25 P (O) (OCH2. CH CH1 5 minutes 110 90 o I 3 0.3 ° / 0 1600C C2H4CllF23 P (O) (OCH2. CH0- CH2) 2 2 minutes 120 1 105 0 in 4 0.25 0 /, 1600C C2H4CllF23 P (O) (OCH2. CH - CH2) 2 2 minutes 110 t 90 o / 2 50-5 ° / o 1500C C2H4CloF2l P (O) (OCH2 CH - CH2) 2 4 minutes 120 1 95 o / 2 6 0.5ovo 1400 C C2H4CF19 P (O) {NOCH2 CM0- CM2) 2 10 minutes 120, 100 o 12 7 10 / o 100 "C C2H4C8F17 P (O) (OCH2. CH - Cd2) 2 5 minutes 100 90 o 12 8 0.80 / 0 145 "C C2M4C7F15 P (O) {NOCH2 CH - CH2 3 minutes 110 90 pulled 9 10 / o emulsion of a polymer of 125 "C CH2 - N (CH3SO, C8F17 10 minutes 90 60 CH2-OCO CH = CH2 (Comparison) 10 1% emulsion of a polymer at 150 "C CH2 N (C3H7) S02 C8F17 4 minutes 90 60 CH2-OCO CH = CH2 (Comparison) Sample 3: The bath also contained 0.10 /, Zn (BF4) 2.

Probe 4: Das Bad enthielt zusätzlich noch 0,050/0 Zn(BF4)2.Sample 4: The bath also contained 0.050/0 Zn (BF4) 2.

Probe 7: Nach dem Tränken und Abquetschen wurden 0,01 0/g Diäthylentriamin, bezogen auf trockenes Stoffgewicht, als 0,5 0/o wäßrige Lösung aufgesprüht.Sample 7: After soaking and squeezing, 0.01% / g diethylenetriamine, Based on the dry weight of the fabric, sprayed on as a 0.5% aqueous solution.

Probe 8: Das Testgewebe war vorher mit 0,30/iger Zirkonacetatlösung getränkt und getrocknet worden.Sample 8: The test fabric was previously with 0.30 / iger zirconium acetate solution soaked and dried.

Probe 9: Das Testgewebe besaß ein Stoffgewicht von 150 g/m² Baumwolle-Zellwolle. Die Harzaufnahme betrug laut Fluoranalyse 0,9 0/o des Trockengewichts des Gewebes.Sample 9: The test fabric had a fabric weight of 150 g / m² cotton-rayon. The resin uptake was 0.9% of the dry weight of the fabric according to fluorine analysis.

Beispiel 1 Zu 15 g CF3 . (CF2)11C2H4 . PO(OH)2, die in 50cm3 Tetrahydrofuran gelöst waren, wurden 4,2 g Epichlorhydrin unter Rühren am Rückfluß innerhalb von 2 Stunden zugetropft. Darauf spaltete man mit 2 g gepulvertem Natriumhydroxyd unter Rühren am Rückfluß Chlorwasserstoff ab. Von dieser Lösung wurden durch Zentrifugieren die unlöslichen Anteile an Salz und Alkali abgetrennt und von der klaren Lösung das Tetrahydrofuran abdestilliert. 17 g Glyzidylester konnten als Rückstand erhalten werden. Example 1 To 15 g of CF3. (CF2) 11C2H4. PO (OH) 2 contained in 50cm3 of tetrahydrofuran were dissolved, 4.2 g of epichlorohydrin were refluxed with stirring within Added dropwise 2 hours. It was then split in with 2 g of powdered sodium hydroxide Stir under reflux from hydrogen chloride. This solution was centrifuged the insoluble fractions of salt and alkali separated and from the clear solution the tetrahydrofuran is distilled off. 17 g of glycidyl ester could be obtained as a residue will.

Die Elementaranalyse ergab folgende Werte: Fluor .. ........... 55,90/0, berechnet 56,50/0 Phosphor .......... 3,6 0/o, berechnet 3,7 0/o. The elemental analysis resulted in the following values: Fluorine .. ........... 55.90 / 0, calculated 56.50 / 0 phosphorus .......... 3.6 0 / o, calculated 3.7 0 / o.

Chlor 0,2 0/o, berechnet 0 0/o. Chlorine 0.2 0 / o, calculated 0 0 / o.

Der Epoxydgehalt wurde nach der Methode von Nicolet, Poulter (Journal of the American Chemical Society, 52, 1930, S. 1186) durch Anlagerung von MCI bestimmt. Dabei wurden 10,8 cm3 n/5-HCl pro Gramm Einwaage verbraucht (berechnet 11,9 cm3/g). The epoxy content was determined using the method of Nicolet, Poulter (Journal of the American Chemical Society, 52, 1930, p. 1186) by the addition of MCI. 10.8 cm3 of n / 5-HCl were used per gram of weight (calculated 11.9 cm3 / g).

In gleicher Weise eingesetzte Phosphonsäure der Formel C10F21C2M4PO(OH)2 ergab den Glyzidylester der Formel mit den Analysenwerten: Fluor ........ ..... 53,6 0/o, berechnet 54,0 0/o.Phosphonic acid of the formula C10F21C2M4PO (OH) 2 used in the same way gave the glycidyl ester of the formula with the analysis values: fluorine ........ ..... 53.6 0 / o, calculated 54.0 0 / o.

Chlor ............ 0,2%, berechnet 00/0. Chlorine ............ 0.2%, calculated 00/0.

Die Epoxydbestimmung ergab einen Verbrauch von 12,0cm3 n/5-HCl pro Gramm Einwaage (berechnet 13,5 0/o). The epoxide determination showed a consumption of 12.0 cm3 n / 5-HCl per Gram weight (calculated 13.5%).

Beispiel 2 10,5 g C8F17 - CM2 - CM2 - PO(OM)2 wurden in 25 cm3 Tetrahydrofuran gelöst. Dazu wurde eine Lösung von 4,2 g Epichlorhydrin in 20cm3 Tetrahydrofuran unter heftigem Rühren bei etwa 500 C zugetropft. 1 Stunde wurde am Rückfluß gekocht, dann wurde diese Lösung zu 1,8 g feingepulvertem Natriumhydroxyd in 20 g Tetrahydrofuran unter kräftigem Rühren bei 35°C innerhalb von 20 Minuten zugetropft. Darauf wurde 10 Minuten lang zum Rückfluß erhitzt. Nach dem Erkalten wurden alle festen Salze abzentrifugiert und das Lösungsmittel abdestilliert. Das so erhaltene Epoxyd wurde in einer Menge von 13 g erhalten und bestand zum größten Teil aus Das Produkt ist eine viskose Flüssigkeit, die in Wasser löslich ist. Die Elementaranalyse ergab folgende Werte: Fluor ....... ....... 52,1 0/o, berechnet 50,5%.Example 2 10.5 g of C8F17 - CM2 - CM2 - PO (OM) 2 were dissolved in 25 cm 3 of tetrahydrofuran. A solution of 4.2 g of epichlorohydrin in 20 cm3 of tetrahydrofuran was added dropwise at about 500 ° C. with vigorous stirring. The mixture was refluxed for 1 hour, then this solution was added dropwise to 1.8 g of finely powdered sodium hydroxide in 20 g of tetrahydrofuran with vigorous stirring at 35 ° C. over the course of 20 minutes. This was followed by refluxing for 10 minutes. After cooling, all solid salts were centrifuged off and the solvent was distilled off. The epoxy thus obtained was obtained in an amount of 13 g and consisted mostly of The product is a viscous liquid that is soluble in water. The elemental analysis gave the following values: Fluorine ....... ....... 52.1 0 / o, calculated 50.5%.

Phosphor ......... 4,70/0, berechnet 4,850/0. Phosphorus ......... 4.70 / 0, calculated 4.850 / 0.

Chlor 0,30/0, berechnet 00/0. Chlorine 0.30 / 0, calculated 00/0.

Bei der Bestimmung des Epoxydgehaltes wurden 14,8 cm3 n/5-HCl pro Gramm Einwaage verbraucht (berechnet 15,6 cm3/g). When determining the epoxy content, 14.8 cm3 n / 5-HCl per Gram weight used up (calculated 15.6 cm3 / g).

Claims (1)

Patentanspruch: Verfahren zur Herstellung von Fluoralkylphosphonsäureglyzidylestern, d a d u r c h g e k e n nzeichnet, daß man in an sich bekannter Weise Perfluoralkylphosphonsäuren der allgemeinen Formel Rf - (CX2)nP(O) (OH)2 in der Rr einen Perfluoralkylrest mit 8 bis 20 Kohlenstoffatomen, X Wasserstoff oder einen Alkylrest und n = 2 oder 3 bedeutet, mit der doppeltmolaren Menge Epichlorhydrin in möglichst wasserfreiem Medium umsetzt und die Chlorhydrinpropylester mit Alkali oder Aminen reagieren läßt. Claim: Process for the production of fluoroalkylphosphonic acid glycidyl esters, d a d u r c h g e n n indicates that perfluoroalkylphosphonic acids are used in a manner known per se of the general formula Rf - (CX2) nP (O) (OH) 2 in which Rr has a perfluoroalkyl radical 8 to 20 carbon atoms, X is hydrogen or an alkyl radical and n = 2 or 3 means with twice the molar amount of epichlorohydrin in as anhydrous as possible Reacts medium and allows the chlorohydrin propyl ester to react with alkali or amines. In Betracht gezogene Druckschriften: Britische Patentschrift Nr. 922 198; USA.-Patentschrift Nr. 2 856 369; Industrial Engineering News, 1. 2. 1960, S. 36. Documents considered: British Patent No. 922 198; U.S. Patent No. 2,856,369; Industrial Engineering News, February 1, 1960, P. 36.
DEB83727A 1964-07-31 1964-07-31 Process for the preparation of fluoroalkylphosphonic acid glycidyl esters Pending DE1254150B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0216271A2 (en) * 1985-09-18 1987-04-01 Röhm Gmbh Phosphonic-acid derivatives for use as adjuvants in leather manufacture

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2856369A (en) * 1953-05-08 1958-10-14 Shell Dev Epoxy-substituted esters of phosphoruscontaining acid and their polymers
GB922198A (en) * 1959-12-18 1963-03-27 Union Carbide Corp Improvements in and relating to phosphorus-containing organic compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2856369A (en) * 1953-05-08 1958-10-14 Shell Dev Epoxy-substituted esters of phosphoruscontaining acid and their polymers
GB922198A (en) * 1959-12-18 1963-03-27 Union Carbide Corp Improvements in and relating to phosphorus-containing organic compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0216271A2 (en) * 1985-09-18 1987-04-01 Röhm Gmbh Phosphonic-acid derivatives for use as adjuvants in leather manufacture
EP0216271A3 (en) * 1985-09-18 1987-11-11 Rohm Gmbh Phosphonic-acid derivatives for use as adjuvants in leather manufacture

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