CA2073359A1 - Process for the preparation of fluorinated polyethers - Google Patents
Process for the preparation of fluorinated polyethersInfo
- Publication number
- CA2073359A1 CA2073359A1 CA 2073359 CA2073359A CA2073359A1 CA 2073359 A1 CA2073359 A1 CA 2073359A1 CA 2073359 CA2073359 CA 2073359 CA 2073359 A CA2073359 A CA 2073359A CA 2073359 A1 CA2073359 A1 CA 2073359A1
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- Prior art keywords
- formula
- ether
- fluoroalkyl
- fluorovinyl
- integer
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
Abstract
Abstract of the disclosure:
Process for the preparation of fluorinated polyethers The invention relates to a process for the preparation of fluorinated polyethers of the formula I
Rf-O-(C2F4)-(C2F4)-O-Rf (I) in which Rf is a straight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical and the two (C2F4) groups, independently of each other, have the structure (CF2-CF2) or (CF(CF3)), from fluorovinyl ethers of the formula II
Rf-O-CF=CF2 (II) in which Rf has the same meaning as in formula I. For this, the liquid fluorovinyl ether (II), or the fluorovinyl ether (II) dissolved in an inert solvent is reacted with gaseous elemental fluorine, which is used undiluted or diluted with an inert gas, at a temperature of from -80 to 200°C.
Process for the preparation of fluorinated polyethers The invention relates to a process for the preparation of fluorinated polyethers of the formula I
Rf-O-(C2F4)-(C2F4)-O-Rf (I) in which Rf is a straight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical and the two (C2F4) groups, independently of each other, have the structure (CF2-CF2) or (CF(CF3)), from fluorovinyl ethers of the formula II
Rf-O-CF=CF2 (II) in which Rf has the same meaning as in formula I. For this, the liquid fluorovinyl ether (II), or the fluorovinyl ether (II) dissolved in an inert solvent is reacted with gaseous elemental fluorine, which is used undiluted or diluted with an inert gas, at a temperature of from -80 to 200°C.
Description
HOECHST AKTIENGESELLSCHAFT HOE 91/F 217 Dr. MAtfe De~cription Proces~ for the preparation of fluorinated polyether~
The invention relates to a process for the preparation of fluorinated polyether~ of the formula I
Rr-O-(C2F4)~(CzF~)~o-Rr ~I) in which R~ is a straight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical and the two (C2~4) groups, independently of each other, have the structure (CFz-CF2) or (CF(CF3)), from fluorovinyl ether~
of the formula II
Rt-O-CF'CF2 (II) in whlch R~ hae the same meaning as in formula I.
Fluorinatod polyether~ are defined by high thermal xo~i~tance, ~tability to aggre~ive chemicals and good compatibility with mo~t working material~. They are therefore preferably u~ed a~ heat conductor~ and test liquids in the electronics sector and in aerospace engineering and also ae nonflammable liquids in chemical proce~ses.
The preparation of fluorinated polyether~ i~ already known, for ex~mple by mean~ of Kolbe electroly~i~
~Japanese Laid Opon Application 58/103 334, German Offenlegung~chrift 3 828 848) or photochemical decar-boxylation of perfluoroether carboxylic acid~(EP-A O 298 863), by pyroly~i~ of perfluoroalkoxyalkyl iodide~ (US Patent 3 657 362) and al~o by reaction of per~luorovinyl ethers with perfluoroacyl fluoride~ and photochemical decarbonylation of the resulting ` ~ - 2 - 20733~9 perfluorinated ketones (German Patent 2 531 511).
However, the working examples in the literature references cited ~how that hydrogen-containing byproduct~
are formed in Kolbe electrolysis, that the pyrolysis of perfluoroalkyl iodides only results in a yield of at most 10 ~, and that the photochemical reactions mentianed only proceed very slowly with reaction times of 16 to 140 h.
It ha~ now been found that the preparation of fluorinated polyethers of the formula I succeeds directly from fluorovinyl ethers of the formula II by fluorination with elemental fluorine.
An object of the invention iB a proces~ for the prepara-tion of fluorinated polyethers of the formula I
Rr-O-(CzF~)~(c2F4t-o-Rr (I) in which Rr i~ a ~traight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical and the two (CzF4) group~, independently of each other, have the ~tructure (CF2-CFz) or (CF(CF3)), from a fluorovinyl ether of the formula I~
Rt-O-CF'CF2 (II) in which Rr ha~ the same meaning a~ in formula I, which comprise~ reacting the liguid fluorovinyl ether (II), or the fluorovinyl ether (II) di~olved in an inert ~olvent, with gaeeou~ elemental fluorine, which i~ used undiluted or tiluted with an inert ga~, at a temperature of from -80 to 200C.
Rr i~ preferably a ~aturated, ~traight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical of the total formula C~Fb-docHd ;, . " ,. ,~ , -. .
_ 3 _ 2~733~9 in which a, b, c, d are integers and a = 2 to 30, b = 4 to 61, c = 0 to 9, d = 0 to 4, in particular d = 0, b + d - 2a or 2a + 1, b - d is 2 4, b/d 2 2 and a/c > 2.
Rt is particularly preferably a radical having the struc-tural formula X-CmF~-(OC3F6)n, in which X - F or H, m is sn integer from 1 to 3 and n i~ an integer from 0 to 9, where m - 3 if n ~ 0. In this context, the case where X
- F is again particularly important.
Rs is in particular a radical of the structural formula C3F~-(OC3FB)~, in which p is an integer from 0 to 8.
To carry out the proce~ according to the invention, the fluorovlnyl ether of the formula II is reacted with gaeeous elemental fluorine, which i~ u~ed undiluted or diluted with an inBrt ga~, for example nitrogen, helium or argon, at a temperature of from -80 to 200C, preferably from -30 to 50C, in particular from -5 to 30C. The fluorovlnyl ether i~ preferably fluorinated without ~olvent, but the fluorination can - if desired -alternatively be carried out in an inert solvent, for example a perfluoropolyether.
~he preparation of the fluorovinyl ethers of the formula II i~ de~cribed in US Patent 2 668 864, U~ Patent 1 145 445, Belgian Patent 840 910, Angew. Chem. Int. ~d.
Engl. 24 (1985), 161-179 and al~o in Ullmann'~
Encyclopedia of Industrial Chemistry, Vol. A 11, Fluorine Compound~, Organic, Chapter 6.2 Perfluorovinyl ~thers, S. 366 ff and the literature references cited there.
_ 4 _ 20733~9 The fluorination is advantageously carried out in a reaction vessel of a fluorine-resistant plastic, for example FEP, PFA, PCTFE or PTFE, the gaseous fluorine being passed through the liquid or dissolved fluorovinyl S ether via a gas frit, for example of PTFE, in the form of finely divided gas bubbles. Complete reaction of the vinyl ether is achieved in these apparatuses.
Dissolved fluorine - which i~ always present in the fluorinations - i5 removed from the reaction mixture present after the fluorination by extraction with aqueous pota~ium hydroxide solution. The fluorinated polyether of the formula (I) is then ~eparated off in pure form by fractional distillation, in vacuo in the case of higher boiling ~ubstances.
The process according to the invention has the following advantages.
1. A fluorinated polyether i~ obtained with defined molecular weight whlch 1~ more than twice that of the fluorovlnyl ether u~ed. Thi~ fluorinated poly-ether, on account of the hlgher molecular weight, po~e~e~ propertie~ which are expedient for the certain applications, for example a higher vlscosity and a very much higher boiling point than that of a fluorinated ether corre~ponding in molecular weight to the fluorovinyl ether.
The invention relates to a process for the preparation of fluorinated polyether~ of the formula I
Rr-O-(C2F4)~(CzF~)~o-Rr ~I) in which R~ is a straight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical and the two (C2~4) groups, independently of each other, have the structure (CFz-CF2) or (CF(CF3)), from fluorovinyl ether~
of the formula II
Rt-O-CF'CF2 (II) in whlch R~ hae the same meaning as in formula I.
Fluorinatod polyether~ are defined by high thermal xo~i~tance, ~tability to aggre~ive chemicals and good compatibility with mo~t working material~. They are therefore preferably u~ed a~ heat conductor~ and test liquids in the electronics sector and in aerospace engineering and also ae nonflammable liquids in chemical proce~ses.
The preparation of fluorinated polyether~ i~ already known, for ex~mple by mean~ of Kolbe electroly~i~
~Japanese Laid Opon Application 58/103 334, German Offenlegung~chrift 3 828 848) or photochemical decar-boxylation of perfluoroether carboxylic acid~(EP-A O 298 863), by pyroly~i~ of perfluoroalkoxyalkyl iodide~ (US Patent 3 657 362) and al~o by reaction of per~luorovinyl ethers with perfluoroacyl fluoride~ and photochemical decarbonylation of the resulting ` ~ - 2 - 20733~9 perfluorinated ketones (German Patent 2 531 511).
However, the working examples in the literature references cited ~how that hydrogen-containing byproduct~
are formed in Kolbe electrolysis, that the pyrolysis of perfluoroalkyl iodides only results in a yield of at most 10 ~, and that the photochemical reactions mentianed only proceed very slowly with reaction times of 16 to 140 h.
It ha~ now been found that the preparation of fluorinated polyethers of the formula I succeeds directly from fluorovinyl ethers of the formula II by fluorination with elemental fluorine.
An object of the invention iB a proces~ for the prepara-tion of fluorinated polyethers of the formula I
Rr-O-(CzF~)~(c2F4t-o-Rr (I) in which Rr i~ a ~traight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical and the two (CzF4) group~, independently of each other, have the ~tructure (CF2-CFz) or (CF(CF3)), from a fluorovinyl ether of the formula I~
Rt-O-CF'CF2 (II) in which Rr ha~ the same meaning a~ in formula I, which comprise~ reacting the liguid fluorovinyl ether (II), or the fluorovinyl ether (II) di~olved in an inert ~olvent, with gaeeou~ elemental fluorine, which i~ used undiluted or tiluted with an inert ga~, at a temperature of from -80 to 200C.
Rr i~ preferably a ~aturated, ~traight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical of the total formula C~Fb-docHd ;, . " ,. ,~ , -. .
_ 3 _ 2~733~9 in which a, b, c, d are integers and a = 2 to 30, b = 4 to 61, c = 0 to 9, d = 0 to 4, in particular d = 0, b + d - 2a or 2a + 1, b - d is 2 4, b/d 2 2 and a/c > 2.
Rt is particularly preferably a radical having the struc-tural formula X-CmF~-(OC3F6)n, in which X - F or H, m is sn integer from 1 to 3 and n i~ an integer from 0 to 9, where m - 3 if n ~ 0. In this context, the case where X
- F is again particularly important.
Rs is in particular a radical of the structural formula C3F~-(OC3FB)~, in which p is an integer from 0 to 8.
To carry out the proce~ according to the invention, the fluorovlnyl ether of the formula II is reacted with gaeeous elemental fluorine, which i~ u~ed undiluted or diluted with an inBrt ga~, for example nitrogen, helium or argon, at a temperature of from -80 to 200C, preferably from -30 to 50C, in particular from -5 to 30C. The fluorovlnyl ether i~ preferably fluorinated without ~olvent, but the fluorination can - if desired -alternatively be carried out in an inert solvent, for example a perfluoropolyether.
~he preparation of the fluorovinyl ethers of the formula II i~ de~cribed in US Patent 2 668 864, U~ Patent 1 145 445, Belgian Patent 840 910, Angew. Chem. Int. ~d.
Engl. 24 (1985), 161-179 and al~o in Ullmann'~
Encyclopedia of Industrial Chemistry, Vol. A 11, Fluorine Compound~, Organic, Chapter 6.2 Perfluorovinyl ~thers, S. 366 ff and the literature references cited there.
_ 4 _ 20733~9 The fluorination is advantageously carried out in a reaction vessel of a fluorine-resistant plastic, for example FEP, PFA, PCTFE or PTFE, the gaseous fluorine being passed through the liquid or dissolved fluorovinyl S ether via a gas frit, for example of PTFE, in the form of finely divided gas bubbles. Complete reaction of the vinyl ether is achieved in these apparatuses.
Dissolved fluorine - which i~ always present in the fluorinations - i5 removed from the reaction mixture present after the fluorination by extraction with aqueous pota~ium hydroxide solution. The fluorinated polyether of the formula (I) is then ~eparated off in pure form by fractional distillation, in vacuo in the case of higher boiling ~ubstances.
The process according to the invention has the following advantages.
1. A fluorinated polyether i~ obtained with defined molecular weight whlch 1~ more than twice that of the fluorovlnyl ether u~ed. Thi~ fluorinated poly-ether, on account of the hlgher molecular weight, po~e~e~ propertie~ which are expedient for the certain applications, for example a higher vlscosity and a very much higher boiling point than that of a fluorinated ether corre~ponding in molecular weight to the fluorovinyl ether.
2. If a (hydrogen-free) perfluorovinyl ether is u~ed, then no hydrogen-containing organic byproduct~ are formed in this reaction, ~ince the only other reactant u~ed i~ fluorine and hydrogen-containing ~olvent~ - which for example are nece~ary for the Kolbe electrolysis mentioned - are not re~uired.
If two different fluorovinyl ether~
R~-0-CF-CFz and R~'-0-CF-CF2 20733~9 are fluorinated together, three different fluorinated polyethers are formed:
Rr-O-(C2F~)-(CzF~)~O-F~
Rr~O~ ( C2F~ ) - ( CzF~ ) ~O~Rr ' and Rr ' -O- ( CzF~ ) - ( CZF~ ) -O-Rf ' ~
where F~ and R~ have the same meaning a~ in formula I.
Thi~ ~oint fluorination is a further ob~ect of the invention.
Examples The percentage~ ~tated denote percentages by weight, unle~ otherwi~e mentioned.
Px~mple 1 The fluorination ~pparatu~ compri~ed a 1 1 FEP ve~sel equipped with a PTFE gas introduction frit. The frit wa~
connected via a T-piece to a fluorine compres~ed gas cyllnder and a nitrogen compres~ed gas cylinder. The fluorlnatlon ve~el wa~ connected to a fluorine absorber filled with ~oda lime. The measurement of the fluorine and nltrogen quantitie~ wa~ carried out u~ing electronic flow meter~ from %a~ting~.
929 g of CaF~-O-CFICFa)-CF2-O-CF-CF2 (2.15 mol) were introduced and were cooled with ice/water to 1 to 3-C.
50.2 l o fluorine (2.24 mol) were pa~ed over the cour~e of 15 h, diluted fluorine being used st the ~tart of the reaction at a concentration of 10 4 by vol (dilu-ted with nitrogen) and pure fluorine being used at the end. During the reaction, the temperature in the reactlon vessel ro~e to 22-C, ~lnce no further cooling agent had been added.
The reaction mixture was then wa~hed twlce with 500 ml of 10 ~ ~trength agueou~ potasslum hydroxlde solutlon each time and once wlth 500 ml of water. 920 g of an organlc phase were obtained, from whlch 245 g of CaP7~(0CaF~)~O~(C2F4)~(C2F4)~0~(C3FgO)-C3F7 with a boiling point of 92C at 10 mbar were isolated at a purity over - . ., 2Q73~59 99 % by fractional di~tillation. The molecular structure of the compound was determined by l~F-NMR spectroscopy.
Example 2 1350 g of C3F~-O-CF(CF3)-CF~-O-CFzCF2 (3.12 mol) were introduced into the apparatus described in Ex~mple 1 and reaeted with 76.2 1 of fluorine (3.40 mol) at a tempera-ture of from 10 to 15-C. The reaction time was 14 h. The fluorine eoneentr~tion at the start of the trial wa~ 40 S
by volume ~dilution with nitrogen). After 5 h, undiluted fluorine waJ u~ed. From the 1364 g of reaction product obtained, 415 g ofC3F7-(OC3F5)-O-(C2F~)-(C2F~)-O-(C3P6O)-C3F7 were obtained after wa~hing with aqueous pota~sium hydroxide ~olution and fraetional di~till~tion.
~xample 3 910 g of C3F,-O-CF(CF3)-CF2-O-CF-CF2 (2.11 mol) were introdueed into the apparatu~ de~eribed in Ex~mple 1.
49.5 1 of fluorine (2.21 mol) were pa~ed in over the eour~e of 6 h, the re~etlon temper~ture being maintained between 22 and 26-C by eooling. The fluorine eoneentra-tlon ~t the ~t~rt of the trial wa~ 30 4 by volume (dilut-ed wlth nltrogen) ~nd w~ lnerea~ed to 100 % by volume after 3 h. 924 g of produet were obtained and were purlfled by wa~hing with 400 ml of 10 4 ~trength potas~lum hydroxide solution and with 350 ml of water.
296 g of C3F7-(OCaFo)~O~(C2F4)~(C2F~)~O~(C3F~O)-C3~7 were obtained by fraetional di~tillation.
~xample 4 125 g of CaY~-O-CF-CP2 ~0.47 mol) were introdueed into a eyllndrleal 250 ml PTFE ve~el and were eooled with iee/water to approximately +l-C. 9 1 of fluorine (0.4 mol), diluted with 40 ~ by volume of nitrogen, were pas~ed in over the eouree of 2 h. The xe~etion mixture wa~ then wa~hed twiee, eaeh time with 50 ml of 10 4 ~trength aqueou~ potas~ium hydroxide ~olution, and then 2073~ ~9 fractionally distilled. 39.5 g of C3F7-O-(c2F4) (C2F4)-O-C3F7 were obtained with a boiling point of 133C.
~he structure of the substance was determined by l~F-NMR
spectroscopy and infrared spectroscopy by comparison with a reference sample.
If two different fluorovinyl ether~
R~-0-CF-CFz and R~'-0-CF-CF2 20733~9 are fluorinated together, three different fluorinated polyethers are formed:
Rr-O-(C2F~)-(CzF~)~O-F~
Rr~O~ ( C2F~ ) - ( CzF~ ) ~O~Rr ' and Rr ' -O- ( CzF~ ) - ( CZF~ ) -O-Rf ' ~
where F~ and R~ have the same meaning a~ in formula I.
Thi~ ~oint fluorination is a further ob~ect of the invention.
Examples The percentage~ ~tated denote percentages by weight, unle~ otherwi~e mentioned.
Px~mple 1 The fluorination ~pparatu~ compri~ed a 1 1 FEP ve~sel equipped with a PTFE gas introduction frit. The frit wa~
connected via a T-piece to a fluorine compres~ed gas cyllnder and a nitrogen compres~ed gas cylinder. The fluorlnatlon ve~el wa~ connected to a fluorine absorber filled with ~oda lime. The measurement of the fluorine and nltrogen quantitie~ wa~ carried out u~ing electronic flow meter~ from %a~ting~.
929 g of CaF~-O-CFICFa)-CF2-O-CF-CF2 (2.15 mol) were introduced and were cooled with ice/water to 1 to 3-C.
50.2 l o fluorine (2.24 mol) were pa~ed over the cour~e of 15 h, diluted fluorine being used st the ~tart of the reaction at a concentration of 10 4 by vol (dilu-ted with nitrogen) and pure fluorine being used at the end. During the reaction, the temperature in the reactlon vessel ro~e to 22-C, ~lnce no further cooling agent had been added.
The reaction mixture was then wa~hed twlce with 500 ml of 10 ~ ~trength agueou~ potasslum hydroxlde solutlon each time and once wlth 500 ml of water. 920 g of an organlc phase were obtained, from whlch 245 g of CaP7~(0CaF~)~O~(C2F4)~(C2F4)~0~(C3FgO)-C3F7 with a boiling point of 92C at 10 mbar were isolated at a purity over - . ., 2Q73~59 99 % by fractional di~tillation. The molecular structure of the compound was determined by l~F-NMR spectroscopy.
Example 2 1350 g of C3F~-O-CF(CF3)-CF~-O-CFzCF2 (3.12 mol) were introduced into the apparatus described in Ex~mple 1 and reaeted with 76.2 1 of fluorine (3.40 mol) at a tempera-ture of from 10 to 15-C. The reaction time was 14 h. The fluorine eoneentr~tion at the start of the trial wa~ 40 S
by volume ~dilution with nitrogen). After 5 h, undiluted fluorine waJ u~ed. From the 1364 g of reaction product obtained, 415 g ofC3F7-(OC3F5)-O-(C2F~)-(C2F~)-O-(C3P6O)-C3F7 were obtained after wa~hing with aqueous pota~sium hydroxide ~olution and fraetional di~till~tion.
~xample 3 910 g of C3F,-O-CF(CF3)-CF2-O-CF-CF2 (2.11 mol) were introdueed into the apparatu~ de~eribed in Ex~mple 1.
49.5 1 of fluorine (2.21 mol) were pa~ed in over the eour~e of 6 h, the re~etlon temper~ture being maintained between 22 and 26-C by eooling. The fluorine eoneentra-tlon ~t the ~t~rt of the trial wa~ 30 4 by volume (dilut-ed wlth nltrogen) ~nd w~ lnerea~ed to 100 % by volume after 3 h. 924 g of produet were obtained and were purlfled by wa~hing with 400 ml of 10 4 ~trength potas~lum hydroxide solution and with 350 ml of water.
296 g of C3F7-(OCaFo)~O~(C2F4)~(C2F~)~O~(C3F~O)-C3~7 were obtained by fraetional di~tillation.
~xample 4 125 g of CaY~-O-CF-CP2 ~0.47 mol) were introdueed into a eyllndrleal 250 ml PTFE ve~el and were eooled with iee/water to approximately +l-C. 9 1 of fluorine (0.4 mol), diluted with 40 ~ by volume of nitrogen, were pas~ed in over the eouree of 2 h. The xe~etion mixture wa~ then wa~hed twiee, eaeh time with 50 ml of 10 4 ~trength aqueou~ potas~ium hydroxide ~olution, and then 2073~ ~9 fractionally distilled. 39.5 g of C3F7-O-(c2F4) (C2F4)-O-C3F7 were obtained with a boiling point of 133C.
~he structure of the substance was determined by l~F-NMR
spectroscopy and infrared spectroscopy by comparison with a reference sample.
Claims (12)
1. A process for the preparation of a fluorinated polyether of the formula I
Rf-O-(C2F4)-(C2F4)-O-Rf (I) in which Rf is a straight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical and the two (C2F4) groups, independently of each other, have the structure (CF2-CF2) or (CF(CF3)), from a fluorovinyl ether of the formula II
Rf-O-CF-CF2 (II) in which Rf has the same meaning as in formula I, which comprises reacting the liquid fluorovinyl ether (II), or the fluorovinyl ether (II) dissolved in an inert solvent, with gaseous elemental fluorine, which is used undiluted or diluted with an inert gas, at a temperature of from -80 to 200°C.
Rf-O-(C2F4)-(C2F4)-O-Rf (I) in which Rf is a straight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical and the two (C2F4) groups, independently of each other, have the structure (CF2-CF2) or (CF(CF3)), from a fluorovinyl ether of the formula II
Rf-O-CF-CF2 (II) in which Rf has the same meaning as in formula I, which comprises reacting the liquid fluorovinyl ether (II), or the fluorovinyl ether (II) dissolved in an inert solvent, with gaseous elemental fluorine, which is used undiluted or diluted with an inert gas, at a temperature of from -80 to 200°C.
2. The process as claimed in claim 1, wherein the radical Rf is a saturated, straight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radical of the total formula CaFb-dOcHd in which a, b, c, d are integers and A = 2 to 30, b = 4 to 61, c = 0 to 9, d = 0 to 4, in particular d - 0, b + d = 2a or 2a + 1, b - d is > 4, b/d > 2 and a/c > 2.
3. The process as claimed in claim 1, wherein the radical Rf has the structural formula X-CmF2m-(OC3F6)n' in which X - F or H, in particular X = F, m is an integer from 1 to 3 and n is an integer from 0 to 9, where m - 3 if n - 0.
4. The process as claimed in claim 1, wherein the radical Rf has the structural formula C3F,-(OC3F6)p, in which p is an integer from 0 to 8.
5. A process for the preparation of a mixture of fluoropolyethers of the formulae I, I' and I"
(I) Rf-O-(C2F4)-(C2F4)-O-Rf, (I') Rf-O-(C2F4)-(C2F4)-O-Rf' and (I") Rf'-O-(C2F4)-(C2F4)-O-R' , in which Rf and Rf' are different from each other, straight-chain, branched or cyclic fluoroalkyl or fluoro-alkyl ether radicals and the (C2F4) groups, independently of each other, have the structure (CF2-CF2) or (CF(CF3)), from a mixture of the fluorovinyl ethers of the formulae II and II' (II) Rf-O-CF-CF2 (II') Rf'-O-CF-CF2 in which Rf and Rf' have the same meaning as in formulae I, I' and I", which comprises reacting the mixture of the fluorovinyl ethers II and II', said mixture being liquid or dissolved in an inert solvent, with gaseous elemental fluorine, which is used undiluted or diluted with an inert gas, at a temperature of from -80 to 200°C.
(I) Rf-O-(C2F4)-(C2F4)-O-Rf, (I') Rf-O-(C2F4)-(C2F4)-O-Rf' and (I") Rf'-O-(C2F4)-(C2F4)-O-R' , in which Rf and Rf' are different from each other, straight-chain, branched or cyclic fluoroalkyl or fluoro-alkyl ether radicals and the (C2F4) groups, independently of each other, have the structure (CF2-CF2) or (CF(CF3)), from a mixture of the fluorovinyl ethers of the formulae II and II' (II) Rf-O-CF-CF2 (II') Rf'-O-CF-CF2 in which Rf and Rf' have the same meaning as in formulae I, I' and I", which comprises reacting the mixture of the fluorovinyl ethers II and II', said mixture being liquid or dissolved in an inert solvent, with gaseous elemental fluorine, which is used undiluted or diluted with an inert gas, at a temperature of from -80 to 200°C.
6. The process as claimed in claim 5, wherein the radicals Rf and Rf' are different from each other, saturated, straight-chain, branched or cyclic fluoroalkyl or fluoroalkyl ether radicals of the total formula CaFb-dOcHd in which a, b, c, d are integers and a = 2 to 30, b = 4 to 61, c = 0 to 9, d = 0 to 4, in particular d = 0, b + d = 2a or 2a + 1, b - d is > 4, b/d > 2 and a/c > 2.
7. The process as claimed in claim 5, wherein the radicals Rf and Rf' are different from each other and have the structural formula X-CmF2m-(OC3F6)n' in which X c F or H, in particular X - F, m is an integer from 1 to 3 and n is an integer from 0 to 9, where m - 3 if n = 0.
8. The process as claimed in claim 5, wherein the radicals Rf and Rf' are different from each other and have the structural formula C3F,-(OC3F6)p, in which p is an integer from 0 to 8.
9. The process as claimed in claim 1, wherein the reaction is carried out at -30 to 50°C.
10. The process as claimed in claim 5, wherein the reaction is carried out at -30 to 50°C.
11. The process as claimed in claim 1, wherein the reaction is carried out at -5 to 30°C.
12. The process as claimed in claim 5, wherein the reaction is carried out at -5 to 30°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4122614.3 | 1991-07-09 | ||
| DE4122614 | 1991-07-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2073359A1 true CA2073359A1 (en) | 1993-01-10 |
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ID=6435705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2073359 Abandoned CA2073359A1 (en) | 1991-07-09 | 1992-07-08 | Process for the preparation of fluorinated polyethers |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0525444A1 (en) |
| JP (1) | JPH05262685A (en) |
| CA (1) | CA2073359A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2716141A (en) * | 1950-12-13 | 1955-08-23 | William T Miller | Preparation of halo aliphatic compounds |
| ATE31188T1 (en) * | 1981-09-08 | 1987-12-15 | Green Cross Corp | PERFLUOROUS CHEMICALS, PROCESSES FOR THEIR PRODUCTION AND THEIR USE AS BLOOD SUBSTITUTE. |
| IT1200604B (en) * | 1985-04-04 | 1989-01-27 | Montefluos Spa | FLUORURATION PROCESS IN LIQUID PHASE OF UNSATURATED COMPOUNDS |
-
1992
- 1992-07-07 EP EP92111460A patent/EP0525444A1/en not_active Withdrawn
- 1992-07-08 CA CA 2073359 patent/CA2073359A1/en not_active Abandoned
- 1992-07-08 JP JP18133992A patent/JPH05262685A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05262685A (en) | 1993-10-12 |
| EP0525444A1 (en) | 1993-02-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |