WO1995011877A1 - Polyfluorinated alcohols and preparation methods thereof - Google Patents

Polyfluorinated alcohols and preparation methods thereof Download PDF

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Publication number
WO1995011877A1
WO1995011877A1 PCT/FR1994/001188 FR9401188W WO9511877A1 WO 1995011877 A1 WO1995011877 A1 WO 1995011877A1 FR 9401188 W FR9401188 W FR 9401188W WO 9511877 A1 WO9511877 A1 WO 9511877A1
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Prior art keywords
alcohols
polyfluorinated
ch2cf2
alcohol
radical
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PCT/FR1994/001188
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French (fr)
Inventor
Pierre Durual
Patrick Lambert
André Lantz
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Elf Atochem S.A.
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Publication of WO1995011877A1 publication Critical patent/WO1995011877A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/34—Halogenated alcohols
    • C07C31/38—Halogenated alcohols containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids

Definitions

  • the present invention relates to the field of functional fluorinated derivatives and more particularly relates to polyfluorinated alcohols usable as intermediates for the manufacture of hydrophobic, oleophobic and anti-fouling agents.
  • fluorinated esters have been described which are derived from mono-, di- or tricarboxylic unsaturated acids, in particular acrylates and methacrylates of formula:
  • Rp represents a perfluorinated radical in 04-0-14, p an integer ranging from 0 to 3, n an integer ranging from 1 to 12 and R a hydrogen atom or a methyl radical.
  • the polymers or copolymers derived from these unsaturated esters are particularly advantageous as a hydrophobic, oleophobic and anti-fouling treatment agent for various supports such as textiles, leather, paper, stone, etc.
  • nitrates used in the previous process are themselves prepared by the action of an excess of concentrated nitric acid on the corresponding iodides RF (CH 2 CF 2 ) pC n H2 n l-
  • This process described in patent FR 2,096 179, also has the very big drawback of releasing elementary iodine which, by subli ⁇ mation, is deposited in all the devices of the installation used, which makes its recovery and cleaning very difficult, if not impossible.
  • the present invention now relates to polyfluorinated alcohols of general formula: RF- (CH 2 CF2) m -CH2CH 2 OH (I)
  • Rp represents a perfluoroalkyl radical and m denotes an integer ranging from 1 to 10.
  • the perfluoroalkyl radical Rp can be linear or branched and contain from 2 to 18 carbon atoms. Particularly preferred are the alcohols in which Rp is linear and contains from 2 to 6 carbon atoms, and especially those in which Rp is the perfluoroethyl radical.
  • alcohols in which the number of CH2CF2 units (m) is between 2 and 6, and more particularly 3 to 5.
  • polyfluorinated alcohols according to the invention can be prepared from the corresponding polyfluoroalkyl iodides of formula:
  • the iodide (II) is reacted with the oleum to form an acid sulfate:
  • the formation of acid sulfate (III) can be carried out in 1 to 2 hours at a temperature ranging from 25 to 95 ° C using 3 to 10 moles of SO3 in the form of oleum 20 to 25% per mole of iodide (II ).
  • the hydrolysis of the acid sulfate (III) can be carried out in 1 to 2 hours at 100 ° C in 2 to 4 times its weight of water added with 1.5 to 2 times the amount of sodium sulfite required to reduce iodine to sodium iodide.
  • the released alcohol (I), insoluble in water can be recovered by decantation (lower phase) or, during the hydrolysis phase, by azeotropic distillation.
  • Another method for preparing the alcohols according to the invention consists in reacting the iodide (II) with an aqueous solution of dimethylformamide, then in hydrolyzing or transesterifying the formate of formula:
  • the first reaction advantageously carried out in 10 to 15 hours at 120-160 ° C using 2 to 8 moles of water and 10 to 40 moles of dimethylformamide per mole of iodide (II), leads to the concomitant formation of alcohol (I) and corresponding formate (IV).
  • the alcohol-formate mixture is isolated before subjecting it to hydrolysis or to a transesterification to transform the formate (IV) into alcohol (I).
  • the hydrolysis can be carried out in 1 to 2 hours at reflux with an alcoholic solution of 1 to 1.5 equivalents of sodium or potassium hydroxide.
  • the transesterification can be carried out with methanol in the presence of an acid catalyst such as, for example, p-toluenesulfonic acid.
  • an acid catalyst such as, for example, p-toluenesulfonic acid.
  • the aqueous solution of dimethylformamide can be replaced by N-methylformamide in an amount of 5 to 15 moles per mole of iodide (II).
  • the iodides (II) used are known products, the production of which is described in French patents 2 103459, 2 220 504, 2220505, 2220515 as well as in European patents 140254 and 142041.
  • the transformation of the polyfluorinated alcohols according to the invention into acrylic or methacrylic esters can be easily carried out by known methods, in particular by direct reaction with acrylic or methacrylic acid in an aromatic solvent in the presence of an acid catalyst , or by transesterification with pacrylate or methyl methacrylate.

Abstract

The invention relates to polyfluorinated alcohols having the formula RF-(CH2CF2)m-CH2CH2OH, wherein RF is a C2-C18 perfluoroalkyl radical and m is an integer from 1 to 10. Said alcohols, prepared from corresponding iodides RF-(CH2CF2)m-CH2CH2l are useful as intermediates for the preparation of hydrophobic, oleophobic and anti-stain agents.

Description

ALCOO S PO YFLUORES ET LEURS PROCEDES DE PREPARATION ALCOO S PO YFLUORES AND THEIR PREPARATION METHODS
La présente invention concerne le domaine des dérivés fluorés fonctionnels et a plus particulièrement pour objet des alcools polyfluorés utilisables comme in- termediaires pour la fabrication d'agents hydrophobes, oleophobes et anti-salissu¬ res.The present invention relates to the field of functional fluorinated derivatives and more particularly relates to polyfluorinated alcohols usable as intermediates for the manufacture of hydrophobic, oleophobic and anti-fouling agents.
Dans le brevet FR 2 200238 on a décrit des esters fluorés dérivés d'acides insaturés mono-, di- ou tricarboxyliques, notamment des acrylates et méthacrylates de formule :In patent FR 2 200238, fluorinated esters have been described which are derived from mono-, di- or tricarboxylic unsaturated acids, in particular acrylates and methacrylates of formula:
RF-(CH2CF2)p-CnH2n-OCOC(R) = CH2 R F - (CH2CF 2 ) pC n H 2 n-OCOC (R) = CH 2
dans laquelle Rp représente un radical perfluoré en 04-0-14, p un nombre entier allant de 0 à 3, n un nombre entier allant de 1 à 12 et R un atome d'hydrogène ou un radical méthyle. Les polymères ou copolymères dérivés de ces esters insaturés sont particulièrement intéressants comme agent de traitement hydrophobe, oléophobe et anti-salissures de supports variés tels que textiles, cuir, papier, pierre, etc..in which Rp represents a perfluorinated radical in 04-0-14, p an integer ranging from 0 to 3, n an integer ranging from 1 to 12 and R a hydrogen atom or a methyl radical. The polymers or copolymers derived from these unsaturated esters are particularly advantageous as a hydrophobic, oleophobic and anti-fouling treatment agent for various supports such as textiles, leather, paper, stone, etc.
Selon le brevet FR 2 200 238, ces esters insaturés sont obtenus par réaction d'un acide insaturé sur un nitrate de formule :According to patent FR 2 200 238, these unsaturated esters are obtained by reaction of an unsaturated acid on a nitrate of formula:
RF-(CH2CF2)p-CnH2n-ONθ2RF- (CH 2 CF2) pC n H2n-ONθ2
en présence d'acide sulfurique concentré dans un solvant aromatique comme le benzène, le toluène ou les xylènes, à une température de 80 à 150°C pendant une durée de 10 à 20 heures. Outre le dégagement de vapeurs nitreuses toujours gê¬ nantes, le gros inconvénient de ce procédé réside dans la formation de nombreux sous-produits, en particulier de dérivés sulfonés et nitrés du solvant aromatique uti¬ lisé. Ces sous-produits nécessitent des traitements de séparation supplémentaires et créent des effluents difficiles à éliminer. Les nitrates utilisés dans le procédé précédent sont eux-mêmes préparés par action d'un excès d'acide nitrique concentré sur les iodures correspondants RF(CH2CF2)pCnH2nl- Ce procédé, décrit dans le brevet FR 2 096 179, présente également le très gros inconvénient de libérer de l'iode élémentaire qui, par subli¬ mation, se dépose dans tous les appareils de l'installation utilisée, ce qui rend sa ré- cupération et les nettoyages très difficiles, sinon impossibles.in the presence of concentrated sulfuric acid in an aromatic solvent such as benzene, toluene or xylenes, at a temperature of 80 to 150 ° C for a period of 10 to 20 hours. In addition to the release of nitrous vapors which are always troublesome, the major drawback of this process lies in the formation of numerous by-products, in particular of sulfonated and nitrated derivatives of the aromatic solvent used. These by-products require additional separation treatments and create effluents that are difficult to remove. The nitrates used in the previous process are themselves prepared by the action of an excess of concentrated nitric acid on the corresponding iodides RF (CH 2 CF 2 ) pC n H2 n l- This process, described in patent FR 2,096 179, also has the very big drawback of releasing elementary iodine which, by subli¬ mation, is deposited in all the devices of the installation used, which makes its recovery and cleaning very difficult, if not impossible.
La présente invention a maintenant pour objet les alcools polyfluorés de formule générale : RF-(CH2CF2)m-CH2CH2OH (I)The present invention now relates to polyfluorinated alcohols of general formula: RF- (CH 2 CF2) m -CH2CH 2 OH (I)
dans laquelle Rp représente un radical perfluoroalkyle et m désigne un nombre entier allant de 1 à 10. La transformation de ces alcools en esters acryliques ou méthacryliques est particulièrement facile et permet d'éviter les inconvénients de la technique antérieure.in which Rp represents a perfluoroalkyl radical and m denotes an integer ranging from 1 to 10. The transformation of these alcohols into acrylic or methacrylic esters is particularly easy and makes it possible to avoid the drawbacks of the prior art.
Dans les alcools polyfluorés selon l'invention, le radical perfluoroalkyle Rp peut être linéaire ou ramifié et contenir de 2 à 18 atomes de carbone. Sont plus par¬ ticulièrement préférés les alcools dans lesquels Rp est linéaire et contient de 2 à 6 atomes de carbone, et surtout ceux dans lesquels Rp est le radical perfluoroéthyle.In the polyfluorinated alcohols according to the invention, the perfluoroalkyl radical Rp can be linear or branched and contain from 2 to 18 carbon atoms. Particularly preferred are the alcohols in which Rp is linear and contains from 2 to 6 carbon atoms, and especially those in which Rp is the perfluoroethyl radical.
Sont également préférés les alcools dans lesquels le nombre de motifs CH2CF2 (m) est compris entre 2 et 6, et plus particulièrement 3 à 5.Also preferred are alcohols in which the number of CH2CF2 units (m) is between 2 and 6, and more particularly 3 to 5.
Les alcools polyfluorés selon l'invention peuvent être préparés à partir des iodures de polyfluoroalkyle correspondants de formule :The polyfluorinated alcohols according to the invention can be prepared from the corresponding polyfluoroalkyl iodides of formula:
RF-(CH2CF2)m-CH2CH2l (II)RF- (CH 2 CF2) m -CH 2 CH 2 l (II)
Selon une première méthode, on fait réagir l'iodure (II) avec l'oléum pour former un sulfate acide :According to a first method, the iodide (II) is reacted with the oleum to form an acid sulfate:
RF-(CH2CF2)m-CH2CH2θSθ3H (III)RF- (CH 2 CF2) m-CH 2 CH2θSθ3H (III)
qu'on hydrolyse ensuite pour former l'alcool (I). La formation du sulfate acide (III) peut être réalisée en 1 à 2 heures à une température allant de 25 à 95°C en utilisant 3 à 10 moles de SO3 sous forme d'oléum 20 à 25 % par mole d'iodure (II). L'hydro¬ lyse du sulfate acide (III) peut être effectuée en 1 à 2 heures à 100°C dans 2 à 4 fois son poids d'eau additionnée de 1,5 à 2 fois la quantité de sulfite de sodium néces¬ saire pour réduire l'iode en iodure de sodium. L'alcool (I) libéré, insoluble dans l'eau, peut être récupéré par décantation (phase inférieure) ou, pendant la phase d'hydro- lyse, par distillation azéotropique.which is then hydrolyzed to form the alcohol (I). The formation of acid sulfate (III) can be carried out in 1 to 2 hours at a temperature ranging from 25 to 95 ° C using 3 to 10 moles of SO3 in the form of oleum 20 to 25% per mole of iodide (II ). The hydrolysis of the acid sulfate (III) can be carried out in 1 to 2 hours at 100 ° C in 2 to 4 times its weight of water added with 1.5 to 2 times the amount of sodium sulfite required to reduce iodine to sodium iodide. The released alcohol (I), insoluble in water, can be recovered by decantation (lower phase) or, during the hydrolysis phase, by azeotropic distillation.
Une autre méthode de préparation des alcools selon l'invention consiste à faire réagir l'iodure (II) avec une solution aqueuse de diméthylformamide, puis à hy- drolyser ou transestérifier le formiate de formule :Another method for preparing the alcohols according to the invention consists in reacting the iodide (II) with an aqueous solution of dimethylformamide, then in hydrolyzing or transesterifying the formate of formula:
RF-(CH2CF2)m-CH2CH2OCOH (IV)RF- (CH2CF2) m-CH 2 CH 2 OCOH (IV)
co-produit en même temps que l'alcool (I). La première réaction, avantageusement réalisée en 10 à 15 heures à 120-160°C en utilisant 2 à 8 moles d'eau et 10 à 40 moles de diméthylformamide par mole d'iodure (II), conduit à la formation concomi¬ tante d'alcool (I) et de formiate (IV) correspondant. Par addition d'eau au mélange réactionnel et décantation, on isole le mélange alcool-formiate avant de le soumettre à une hydrolyse ou à une transesterification pour transformer le formiate (IV) en alcool (I). L'hydrolyse peut être réalisée en 1 à 2 heures à reflux avec une solution alcoolique de 1 à 1 ,5 équivalent d'hydroxyde de sodium ou de potassium. La tran¬ sesterification peut être effectuée avec le méthanol en présence d'un catalyseur acide comme, par exemple, l'acide p-toluènesulfonique. Après l'étape d'hydrolyse ou de transesterification, l'addition d'eau suivie d'une décantation et d'une distillation de la phase inférieure permet de récupérer l'alcool (I).co-produced at the same time as alcohol (I). The first reaction, advantageously carried out in 10 to 15 hours at 120-160 ° C using 2 to 8 moles of water and 10 to 40 moles of dimethylformamide per mole of iodide (II), leads to the concomitant formation of alcohol (I) and corresponding formate (IV). By adding water to the reaction mixture and decanting, the alcohol-formate mixture is isolated before subjecting it to hydrolysis or to a transesterification to transform the formate (IV) into alcohol (I). The hydrolysis can be carried out in 1 to 2 hours at reflux with an alcoholic solution of 1 to 1.5 equivalents of sodium or potassium hydroxide. The transesterification can be carried out with methanol in the presence of an acid catalyst such as, for example, p-toluenesulfonic acid. After the hydrolysis or transesterification step, the addition of water followed by decantation and distillation of the lower phase makes it possible to recover the alcohol (I).
Dans cette seconde méthode de préparation des alcools polyfluorés selon l'invention, on peut remplacer la solution aqueuse de diméthylformamide par le N- méthylformamide à raison de 5 à 15 moles par mole de iodure (II).In this second method for preparing the polyfluorinated alcohols according to the invention, the aqueous solution of dimethylformamide can be replaced by N-methylformamide in an amount of 5 to 15 moles per mole of iodide (II).
Les iodures (II) utilisés sont des produits connus dont l'obtention est décrite dans les brevets français 2 103459, 2 220 504, 2220505, 2220515 ainsi que dans les brevets européens 140254 et 142041.The iodides (II) used are known products, the production of which is described in French patents 2 103459, 2 220 504, 2220505, 2220515 as well as in European patents 140254 and 142041.
La transformation des alcools polyfluorés selon l'invention en esters acryli¬ ques ou méthacryliques peut être facilement réalisée par les méthodes connues, en particulier par réaction directe avec l'acide acrylique ou méthacrylique dans un sol- vant aromatique en présence d'un catalyseur acide, ou encore par transesterification avec Pacrylate ou le méthacrylate de méthyle.The transformation of the polyfluorinated alcohols according to the invention into acrylic or methacrylic esters can be easily carried out by known methods, in particular by direct reaction with acrylic or methacrylic acid in an aromatic solvent in the presence of an acid catalyst , or by transesterification with pacrylate or methyl methacrylate.
Les exemples suivants illustrent l'invention sans la limiter. Sauf indication contraire, les pourcentages indiqués sont exprimés en poids.The following examples illustrate the invention without limiting it. Unless otherwise indicated, the percentages indicated are expressed by weight.
EXEMPLE 1EXAMPLE 1
Dans un réacteur en verre de 4 litres, muni de dispositifs de chauffage et d'agitation, on a chargé 1510 g de l'iodure polyfluoré C2F5-(CH2CF2)3-CH2CH2l à 97,9 % de pureté et 1456 g de N-méthylformamide, puis on a chauffé sous agitation pendant 30 heures à 150°C. Après avoir refroidi le mélange jusqu'à 80°C, on l'a lavé deux fois avec 1 litre d'eau à 80°C et, après décantation, on a récupéré la phase organique inférieure (1192 g) ayant la composition suivante (analyse par chromatographie phase gaz) :1510 g of polyfluorinated iodide C2F5- (CH2CF2) 3-CH2CH2l at 97.9% purity and 1456 g of N- were charged into a 4-liter glass reactor equipped with heating and stirring devices. methylformamide, then heated with stirring for 30 hours at 150 ° C. After having cooled the mixture to 80 ° C., it was washed twice with 1 liter of water at 80 ° C. and, after decantation, the lower organic phase (1192 g) having the following composition was recovered ( gas phase chromatography analysis):
- alcool C2F5-(CH2CF2)3-CH2CH2OH 24 % - formiate de cet alcool 63,5 %- alcohol C2F5- (CH2CF 2 ) 3-CH2CH 2 OH 24% - formate of this alcohol 63.5%
- oléfine C2F5-(CH2CF2)3-CH = CH2 4 %- olefin C 2 F5- (CH 2 CF 2 ) 3-CH = CH 2 4%
- iodure de départ 0,8 % Dans un réacteur de deux litres, on a charge 1167 g de ce mélange avec 388 ml de méthanol et 11 g d'acide paratoluènesulfonique, puis on a distillé le for¬ miate de méthyle formé. On a arrêté la distillation quand le méthanol a commencé à distiller, puis on a ajouté au réacteur une solution de 10 g d'hydroxyde de potassium en pastilles dans 280 ml de méthanol et on a porté le mélange au reflux pendant 2 heures.- starting iodide 0.8% 1167 g of this mixture are charged into a two-liter reactor with 388 ml of methanol and 11 g of paratoluenesulfonic acid, then the methyl formate formed is distilled. The distillation was stopped when the methanol started to distill, then a solution of 10 g of potassium hydroxide pellets in 280 ml of methanol was added to the reactor and the mixture was brought to reflux for 2 hours.
Le mélange a ensuite été lavé deux fois avec 1 ,2 litre d'eau à 90°C. Après décantation, on a récupéré 1073 g de phase organique inférieure qui, par distillation sous vide, a fourni 896 g d'un produit distillant à 114°C sous 4 mbar et présentant un point de fusion de 59°C.The mixture was then washed twice with 1.2 liters of 90 ° C water. After decantation, 1073 g of lower organic phase were recovered which, by vacuum distillation, provided 896 g of a product distilling at 114 ° C under 4 mbar and having a melting point of 59 ° C.
L'analyse de ce produit par couplage CG/SM a donné les résultats suivants :Analysis of this product by CG / SM coupling gave the following results:
C2F5-(CH2CF2)3-CH2CH2OH 96 %C2F5- (CH 2 CF2) 3-CH2CH 2 OH 96%
C2F5-(CH2CF2)2-CH2CF = CH-CH2OH 1,6 % C2F5-(CH2CF2)2-CH(CH2)2-CF2 1,2 %C2F5- (CH2CF 2 ) 2-CH 2 CF = CH-CH 2 OH 1.6% C2F5- (CH 2 CF2) 2-CH (CH2) 2-CF 2 1.2%
I 0 1I 0 1
C2F5-(CH2CF2)3-CH2CH2I : 0,8 %C2F5- (CH 2 CF 2 ) 3-CH2CH 2 I: 0.8%
et l'analyse par RMN 1H, 13C et 19F a confirmé la structure de l'alcool.and 1 H, 13 C and 19 F NMR analysis confirmed the structure of the alcohol.
EXEMPLE 2EXAMPLE 2
Dans un réacteur, on a chargé 1515 g de l'iodure C2F5~(CH2CF2)4- CH2CH2I à 94,6 % de pureté, 2550 g de diméthylformamide et 100 g d'eau, puis le mélange a été chauffé pendant 14 heures à reflux. Après dilution avec 600 ml d'eau, on a soutiré la phase organique inférieure et on l'a lavée deux fois avec 700 ml d'eau à 90°C. Après décantation, on a ajouté à la phase organique une solution de 85 g d'hydroxyde de sodium dans 1300 g d'éthanol, puis le mélange a été chauffé à reflux pendant une heure.1515 g of iodide C2F5 ~ (CH2CF2) 4- CH2CH2I at 94.6% purity, 2550 g of dimethylformamide and 100 g of water were charged into a reactor, then the mixture was heated for 14 hours at reflux. After dilution with 600 ml of water, the lower organic phase was drawn off and washed twice with 700 ml of water at 90 ° C. After decantation, a solution of 85 g of sodium hydroxide in 1300 g of ethanol was added to the organic phase, then the mixture was heated at reflux for one hour.
Après dilution avec 3 litres d'eau, la phase inférieure a été soutirée, puis la- vée deux fois avec 1 ,5 litres d'eau à 90°C et soutirée à nouveau. Par distillation sous vide de cette phase organique (1070 g), on a obtenu 660 g d'un produit distillant à 123°C sous 1 mbar et présentant un point de fusion de 75°C.After dilution with 3 liters of water, the lower phase was withdrawn, then washed twice with 1.5 liters of water at 90 ° C. and withdrawn again. By vacuum distillation of this organic phase (1070 g), 660 g of a product distilled at 123 ° C. under 1 mbar and having a melting point of 75 ° C. was obtained.
Son analyse chromatographique a donné les résultats suivants :Its chromatographic analysis gave the following results:
C2F5-(CH2CF2)4-CH2CH2OH : 97,2 %C 2 F5- (CH2CF2) 4-CH2CH 2 OH: 97.2%
C2F5-(CH2CF2)3-CH2CF = CH-CH2OH : 1 ,4 %C2F5- (CH 2 CF 2 ) 3-CH 2 CF = CH-CH 2 OH: 1.4%
et l'analyse par RMN 1H, 13C et 19F a confirmé la structure de l'alcool. EXEMPLE 3and 1 H, 13 C and 19 F NMR analysis confirmed the structure of the alcohol. EXAMPLE 3
En opérant comme à l'exemple 1 à partir de 1355 g de l'iodure C2F5- (CH2CF2)δ-CH2CH2l et 1000 g de N-méthylformamide, on a obtenu 1278 g d'alcool brut dont la distillation sous vide a fourni 660 g d'un produit distillant à 158°C sous 1 mbar et fondant à 89°C.By operating as in Example 1 from 1355 g of iodide C2F5- (CH2CF2) δ-CH2CH2l and 1000 g of N-methylformamide, 1278 g of crude alcohol were obtained, the vacuum distillation provided 660 g of a product distilling at 158 ° C under 1 mbar and melting at 89 ° C.
L'analyse chromatographique de ce produit a donné les résultats suivants :The chromatographic analysis of this product gave the following results:
C2F5-(CH2CF2)5-CH2CH2θH : 93,8 %C2F5- (CH 2 CF2) 5-CH 2 CH2θH: 93.8%
C2F5-(CH2CF2) -CH2CF ≈ CH-CH2OH : 4,2 %C 2 F5- (CH 2 CF2) -CH2CF ≈ CH-CH 2 OH: 4.2%
et l'analyse par RMN 1H, 13c et 19F a confirmé la structure attendue. and 1 H, 13c and 19 F NMR analysis confirmed the expected structure.

Claims

REVENDICATIONS
1. Alcools polyfluorés de formule générale :1. Polyfluorinated alcohols of general formula:
RF-(CH2CF2)m-CH2CH2θHRF- (CH 2 CF2) m-CH 2 CH2θH
dans laquelle Rp désigne un radical perfluoroalkyle, linéaire ou ramifié, de 2 à 18 atomes de carbone et m représente un nombre entier allant de 1 à 10.in which Rp denotes a linear or branched perfluoroalkyl radical of 2 to 18 carbon atoms and m represents an integer ranging from 1 to 10.
2. Alcools selon la revendication 1 , dans lesquels m est un nombre entier allant de 2 à 6, de préférence 3 à 5.2. Alcohols according to claim 1, in which m is an integer ranging from 2 to 6, preferably 3 to 5.
3. Alcools selon la revendication 1 ou 2, dans lesquels Rp est un radical linéaire contenant 2 à 6 atomes de carbone, de préférence le radical perfluoroéthyle.3. Alcohols according to claim 1 or 2, in which Rp is a linear radical containing 2 to 6 carbon atoms, preferably the perfluoroethyl radical.
4. Procédé de préparation d'un alcool polyfluore selon l'une des revendica¬ tions 1 à 3, caractérisé en ce que l'on fait réagir l'iodure polyfluore correspondant Rp-(CH2CF2) ~CH2CH2l avec l'oléum, puis on hydrolyse le sulfate acide ainsi ob¬ tenu.4. Process for preparing a polyfluorinated alcohol according to one of claims 1 to 3, characterized in that the corresponding polyfluorodiodide Rp- (CH2CF2) ~ CH2CH2l is reacted with oleum, then hydrolyzes the acid sulfate thus obtained.
5. Procédé de préparation d'un alcool polyfluore selon l'une des revendica¬ tions 1 à 3, caractérisé en ce que l'on fait réagir l'iodure polyfluore correspondant5. Process for the preparation of a polyfluorinated alcohol according to one of claims 1 to 3, characterized in that the corresponding polyfluorodiodide is reacted
RF-(CH2CF2)rτrCH2CH2l avec une solution aqueuse de diméthylformamide ou avec le N-méthylformamide, puis on hydrolyse ou transestérifie le formiate Rp- (CH2CF2)m-CH2CH2θCOH co-produit. RF- ( CH 2CF2) rτr CH 2 CH 2l with an aqueous solution of dimethylformamide or with N-methylformamide, then the formate Rp- (CH2CF2) m -CH 2 CH2θCOH is hydrolyzed or transesterified.
PCT/FR1994/001188 1993-10-27 1994-10-13 Polyfluorinated alcohols and preparation methods thereof WO1995011877A1 (en)

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