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
- Authority
- CA
- Canada
- Prior art keywords
- formula
- ether
- fluoroalkyl
- fluorovinyl
- integer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229920000570 polyether Polymers 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- 239000011737 fluorine Substances 0.000 claims abstract description 22
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 claims abstract description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002170 ethers Chemical class 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000012442 inert solvent Substances 0.000 claims abstract description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000011261 inert gas Substances 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000003682 fluorination reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 244000228957 Ferula foetida Species 0.000 description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
- 238000006576 Kolbe electrolysis reaction Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- -1 perfluoroalkyl iodides Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 239000008207 working material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 |
|---|---|---|---|
| DE4122614 | 1991-07-09 | ||
| DEP4122614.3 | 1991-07-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2073359A1 true CA2073359A1 (en) | 1993-01-10 |
Family
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 |
| EP0077114B1 (en) * | 1981-09-08 | 1987-12-02 | Green Cross Corporation | Perfluorochemicals, process for preparing the same and their use as blood substitutes |
| 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 JP JP18133992A patent/JPH05262685A/en not_active Withdrawn
- 1992-07-08 CA CA 2073359 patent/CA2073359A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0525444A1 (en) | 1993-02-03 |
| JPH05262685A (en) | 1993-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100386824B1 (en) | Process for preparing hydrogen-terminated polyoxyperfluoroalkanes | |
| KR840001980B1 (en) | Process for the preparation of acid fluorides and resulting monomers | |
| US6225511B1 (en) | Synthesis of fluorinated ethers | |
| EP3822256B1 (en) | Vinylsulfonic anhydride, method for producing same, and method for producing vinylsulfonyl fluoride | |
| CN109574812B (en) | Method for preparing perfluoroolefin with high selectivity | |
| IT9020920A1 (en) | PROCESS FOR THE PREPARATION OF PERFLUOROALCOXYSULPHONIC COMPOUNDS | |
| CA2164604A1 (en) | Process for preparing perfluoroalkanesulfonyl fluorides | |
| EP2484662A1 (en) | Method for producing perfluorosulfonic acid having ether structure and derivative thereof, and surfactant containing fluorine-containing ether sulfonic acid compound and derivative thereof | |
| KR100758163B1 (en) | Processes for the preparation of fluorinated acyl fluorides and fluorinated vinyl ethers | |
| US7408019B2 (en) | Fluorinated ether compound | |
| CA2073359A1 (en) | Process for the preparation of fluorinated polyethers | |
| US6936722B2 (en) | Polyhalogenated ethers | |
| KR20140004680A (en) | Process for producing fluorinated organic compounds | |
| EP3436424B1 (en) | Method for the manufacture of fluorinated compounds | |
| US5474657A (en) | Preparation of F-alkyl F-isobutyl ethers by electrochemical fluorination | |
| WO2015014735A1 (en) | Fluorinated compounds containing a -osf5 group and process for their preparation | |
| US20140339096A1 (en) | Method for producing perfluorosulfonic acid having ether structure and derivative thereof, and surfactant containing fluorine-containing ether sulfonic acid compound and derivative thereof | |
| US3882178A (en) | Fluorinated tertiary amino ethers | |
| US6150565A (en) | Process using CF2 I2 and olefins for producing diiodo fluorocompounds, and products thereof | |
| KR101125167B1 (en) | Process for preparing fluorohalogenethers | |
| US20050014969A1 (en) | Process for producing perfluorovinylcarboxylic acid ester | |
| Hung et al. | Synthesis of perfluorovinyl ether monomers | |
| EP0736524A2 (en) | Process for the synthesis of fluorinated alkyl sulphonyl halides | |
| EP1325906B1 (en) | Alkyl esters of 2-(2-fluorosulphonyl)-perfluoroethylenoxy-3-halogen-propionic acid | |
| US20230322661A1 (en) | Synthesis of N,N-Branched Sulfamoyl Fluoride Compounds Using Bismuth Trifluoride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |