DE2319078C3 - Process for the production of practically fluoride-free perfluoroalkane sulfonates - Google Patents
Process for the production of practically fluoride-free perfluoroalkane sulfonatesInfo
- Publication number
- DE2319078C3 DE2319078C3 DE19732319078 DE2319078A DE2319078C3 DE 2319078 C3 DE2319078 C3 DE 2319078C3 DE 19732319078 DE19732319078 DE 19732319078 DE 2319078 A DE2319078 A DE 2319078A DE 2319078 C3 DE2319078 C3 DE 2319078C3
- Authority
- DE
- Germany
- Prior art keywords
- fluoride
- sulfonate
- hydrolysis
- inorganic
- production
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 7
- 150000003871 sulfonates Chemical class 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910001506 inorganic fluoride Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 4
- 230000000875 corresponding Effects 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- VXGBZYAUEMKCDB-UHFFFAOYSA-N fluoro butane-1-sulfonate;potassium Chemical compound [K].CCCCS(=O)(=O)OF VXGBZYAUEMKCDB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N Perfluorooctanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 claims 5
- 150000007513 acids Chemical class 0.000 claims 3
- 150000001768 cations Chemical class 0.000 claims 3
- 150000007529 inorganic bases Chemical class 0.000 claims 3
- -1 Perfluoro Chemical group 0.000 claims 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 125000004432 carbon atoms Chemical group C* 0.000 claims 2
- 230000009089 cytolysis Effects 0.000 claims 2
- 150000004679 hydroxides Chemical class 0.000 claims 2
- 230000002934 lysing Effects 0.000 claims 2
- 229920000515 polycarbonate Polymers 0.000 claims 2
- 239000004417 polycarbonate Substances 0.000 claims 2
- 238000002360 preparation method Methods 0.000 claims 2
- IYRWEQXVUNLMAY-UHFFFAOYSA-N Carbonyl fluoride Chemical class FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 claims 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N Fluorosulfuric acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N HF Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims 1
- 238000005903 acid hydrolysis reaction Methods 0.000 claims 1
- UAWBWGUIUMQJIT-UHFFFAOYSA-N azanium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound N.OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UAWBWGUIUMQJIT-UHFFFAOYSA-N 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 230000005591 charge neutralization Effects 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 231100000078 corrosive Toxicity 0.000 claims 1
- 231100001010 corrosive Toxicity 0.000 claims 1
- 238000006115 defluorination reaction Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 claims 1
- BKONEFQLBOSEEK-UHFFFAOYSA-N fluoroform;potassium Chemical compound [K].FC(F)F BKONEFQLBOSEEK-UHFFFAOYSA-N 0.000 claims 1
- 238000005755 formation reaction Methods 0.000 claims 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 1
- 230000002209 hydrophobic Effects 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- 239000010985 leather Substances 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 230000001264 neutralization Effects 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 125000001477 organic nitrogen group Chemical group 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000000123 paper Substances 0.000 claims 1
- 230000000704 physical effect Effects 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- 150000003460 sulfonic acids Chemical class 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 230000002194 synthesizing Effects 0.000 claims 1
- 239000004753 textile Substances 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- 238000010992 reflux Methods 0.000 description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000005712 crystallization Effects 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L Calcium fluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- OBTWBSRJZRCYQV-UHFFFAOYSA-N Sulfuryl fluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001674 calcium compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OYPRJOBELJOOCE-OUBTZVSYSA-N Calcium-41 Chemical compound [41Ca] OYPRJOBELJOOCE-OUBTZVSYSA-N 0.000 description 1
- 125000000659 L-selenomethionine group Chemical group [H]N([H])[C@]([H])(C(=O)[*])C([H])([H])C([H])([H])[Se]C([H])([H])[H] 0.000 description 1
- 229950003332 Perflubutane Drugs 0.000 description 1
- KAVGMUDTWQVPDF-UHFFFAOYSA-N Perfluorobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)F KAVGMUDTWQVPDF-UHFFFAOYSA-N 0.000 description 1
- 229940077747 antacids containing calcium compounds Drugs 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 229940043430 calcium compounds Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- SLVAEVYIJHDKRO-UHFFFAOYSA-N trifluoromethanesulfonyl fluoride Chemical compound FC(F)(F)S(F)(=O)=O SLVAEVYIJHDKRO-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Description
Bei der Verwendung von Calciumverbindungen in Systeme die Löslichkeit des Sulfonats im Reaktious-When using calcium compounds in systems, the solubility of the sulfonate in the reactive
Form von Calciumoxid oder -hydroxid, bei der medium innerhalb entsprechender Grenzen beliebigForm of calcium oxide or hydroxide, with the medium arbitrary within appropriate limits
naturgemäß keine Fremdanionen in das Reaktionsgut erhöht werden kann, so daß die Abtrennung vomnaturally no foreign anions can be increased in the reaction mixture, so that the separation of the
gelangen, wird durch Bindung von einem Mol Fluorid- Calciumfluorid stets möglich ist. Dies gilt insbesonderereach is always possible by binding one mole of fluoride-calcium fluoride. This is especially true
anion als schwerlösliches Calciumfluorid jeweils ein 5 für längerkettige Perfluoralkansulfonate, die mitanion as a sparingly soluble calcium fluoride each a 5 for longer-chain perfluoroalkanesulfonates, which with
Hydroxidionenäquivalent für_ die weitere Verseifung wachsender Kettenlänge verminderte Löslichkeit inHydroxide ion equivalent for the further saponification of increasing chain length, reduced solubility in
zur Verfügung gestellt. Das Äquivalentverhältnis von Wasser, selbst bei höheren Temperaturen, aufweisen.made available. Have the equivalent ratio of water, even at higher temperatures.
Primärbase zu Calciumhydroxid darf demnach nicht Anhand der folgenden Beispiele soll nunmehr dasThe primary base to calcium hydroxide must therefore not be based on the following examples
größer als lsein. Allerdings wird bei einem genau ein- erfindungsgemäße Verfahren noch näher erläutertgreater than lbe. However, a method according to the invention will be explained in greater detail in the case of a precisely one method
gehaltenen Äquivalentverhältnis von 1 nur selten eine io werdea:
optimale Entfluoridierung erreicht, so daß meist einMaintained equivalent ratio of 1 only rarely becomes an io:
optimal Entfluoridierung achieved, so that mostly a
Überschuß entsprechend einem Äquivalentverhältnis B e i s ο i e 1 1
Primärbase zu Calciumverbindung kleiner als 1 not-Excess corresponding to an equivalent ratio B is ο ie 1 1
Primary base to calcium compound less than 1 necessary
wendig ist. Das optimale Verhältnis muß wegen der Kaliumperfiuorbutansulfonatis agile. The optimal ratio must be because of the potassium perfluorobutanesulfonate
unterschiedlichen Reinheit der eingesetzten Reak- 15different purities of the reac- 15
tanten, insbesondere des Perfluoralkansulfonylfluorids, 1201 Edelwasser bzw. Mutterlauge wurden in einenaunts, especially of the perfluoroalkanesulfonyl fluoride, 1201 noble water or mother liquor were in one
empirisch ermittelt werden. 2501 fassenden Rührkessel gepumpt und unter Rührencan be determined empirically. 2501 stirred kettle pumped and stirring
Das Sulfonylfluorid wird, z.B. über regulierbare 12,6 kg (0,2 K-MoI 100 %iges KOH) Kaliumhydroxid-The sulfonyl fluoride is, e.g. via adjustable 12.6 kg (0.2 K-MoI 100% KOH) potassium hydroxide
DosierjMimpen, in den Reaktionskessel zu der vor- schuppen und 6,5 kg (0,105 K-MoI 100%iges CaO)DosierjMimpen, in the reaction kettle to the pre- and 6.5 kg (0.105 K-MoI 100% CaO)
gelegten Lösung entsprechender Basen mit einer ao Calciumoxid zugegeben. Der Kessel wurde gut ge-added solution of appropriate bases with an ao calcium oxide. The boiler was well
solchen Geschwindigkeit eindosiert, daß gerade noch schlossen und auf eine Temperatur zwischen 85 unddosed at such a rate that just closed and to a temperature between 85 and
ein kleiner Rückfluß gegeben ist. Die Reaktions- 9O0C gebracht. Anschließend wurde Perfluorbutan-there is a small reflux. The reaction 9O brought 0C. Then perfluorobutane
geschwindigkeit ist naturgemäß auch von den appa- sulfonylfluorid mit einer Geschwindigkeit von 1 bisspeed is naturally also of the appasulfonyl fluoride with a speed of 1 to
rativen Gegebenheiten abhängig, im einzelnen auch 1,5 kg pro Stunde durch ein in die vorgelegte Flüssig-depending on the circumstances, in particular also 1.5 kg per hour by pouring into the presented liquid
von der Intensität der Durchmischung, so daß die as keit hineinragendes Einspeisungsrohr zudosiert, so daßof the intensity of the mixing, so that the as speed protruding feed pipe is metered in, so that
Zudosiergeschwindigkeit des Sulfonylfluorids jeweils möglichst wenig Rückfluß dabei entstand. NachdemThe rate of addition of the sulfonyl fluoride resulted in as little reflux as possible. After
empirisch, im Einklang mit den übrigen Parametern etwa 55 kg C4F9SO2F (bezogen auf 100 %iges Produkt)empirically, in accordance with the other parameters about 55 kg C 4 F 9 SO 2 F (based on 100% product)
der Reaktionsführung, etwa der Reaktionstemperatur, zugegeben waren, wurde der pH-Wert der Reaktions-the reaction, about the reaction temperature, were added, the pH of the reaction
gefunden wird. Die optimale Reaktionstemperatur lösung laufend geprüft und so lange weiter zudosiert,Is found. The optimal reaction temperature solution is continuously checked and added as long as
liegt bevorzugt im Bereich zwischen 20 und 1000C, ist 30 bis der pH-Wert bei ungefähr 7,5 lag. Der Gesamt-is preferably in the range between 20 and 100 0 C, is 30 until the pH was about 7.5. The overall
aber auf diesen Temperaturbereich nicht beschränkt verbrauch an 100%igem Sulfonylfluorid betrug 58,8kgbut not restricted to this temperature range. Consumption of 100% sulfonyl fluoride was 58.8 kg
und kann beliebige Werte zwischen 0 und 250° C an- (0,198 K-MoI C4F9SO2F). Der Kesselinhalt wurdeand can accept any value between 0 and 250 ° C (0.198 K-MoI C 4 F 9 SO 2 F). The boiler content was
nehmen. sodann über eine Heißfilterpresse bei 900C vom CaF2 to take. then via a hot filter press at 90 0 C of CaF 2
Die Zugabe der Calciumverbmdung kann sowohl abfiltriert und in den mit Mutterlauge gereinigtenThe addition of the calcium compound can be filtered off and purified with mother liquor
vor, während als auch nach der Hydrolysereaktion 35 Rührkessel zur Kristallisation zurückgepumpt. Beibefore, during and after the hydrolysis reaction 35 stirred kettles are pumped back for crystallization. at
dem Gemisch zugegeben werden. Die Calciumverbin- 200C wurde der entstandene Kristallbrei kaltfiltriert,be added to the mixture. The Calciumverbin- 20 0 C, the resulting crystal slurry was cold-filtered,
dung wird jedoch vorteilhaft bereits zu Beginn der Der feuchte Kuchen enthält durchschnittlich nochThe moist cake still contains on average
Hydrolyse dem Reaktionsgut zugegeben. Überraschen- etwa 5 bis 20% Wasser, das bei 1100C oder imHydrolysis added to the reaction mixture. Surprisingly about 5 to 20% water, which is at 110 0 C or im
derweise werden hier Calciumfluorid-Niederschläge Vakuumtrockenschrank bei tieferer Temperatur ent-calcium fluoride precipitates are formed here in a vacuum drying cabinet at a lower temperature.
erhallen, die ohne Schwierigkeit mit Hilfe geläufiger 40 fernt werden kann. Zurück bleibt ein weißes Pulver anthat can be removed without difficulty with the help of common 40. A white powder remains
Filtrationsverfahren filtriert werden können. hochreinem Kaliumperfluorbutansulfonat.Filtration process can be filtered. high purity potassium perfluorobutane sulfonate.
Die Abtrennungsbedingungen des in Wasser oder
wäßrig-organischen Systemen schwerlöslichen Fluo- Gehalt an anorganischem Fluorid 0,0006% F-The separation conditions of the in water or
Aqueous-organic systems sparingly soluble fluo- content of inorganic fluoride 0.0006% F-
rids vom jeweiligen perfluoralkansulfonsaurem Salz <~«.t,«u .,„ r^i«:„™ η ro»/rids of the respective perfluoroalkanesulfonic acid salt <~ «.t,« u., "r ^ i": "™ η ro" /
... · ν · * τ · · lj τ ·. ι· 11 · Gehalt an Calcium U1O/ /0 ... · ν · * τ · lj τ ·. ι · 11 · Calcium content U 1 O / / 0
richten sich in erster Linie nach dem Loshchkeits- 45 ^, ...are based primarily on the Loshchkeit- 45 ^, ...
verhalten des Sulfonats und müssen gegebenenfalls Kaliumanalysebehavior of the sulfonate and may need potassium analysis
empirisch ermittelt werden. Im allgemeinen geschieht gefunden 11,5 /0 can be determined empirically. Generally found happens 11.5 / 0
die Abtrennung einfach durch Filtration des Calcium- berechnet 11,3 Λthe separation simply by filtration of the calcium calculated 11.3 Λ
fluoride bei jener Temperatur, bei der das Sulfonatfluoride at the temperature at which the sulfonate
gut löslich ist. Die Isolierung des Sulfonats erfolgt 5° Ausbeute: 64,2 kg C4F9SO3 -K+, das entspricht 96%
dann durch anschließende Kristallisation bei tieferen der Theorie; Löslichkeitsprodukt für CaF2 = 3,4 ·
Temperaturen oder durch Verdampfen des Lösungs- 10"» (18° C).
mittels. Da die Mutterlauge immer wieder neu eingesetzt werden kann, ist im Falle der Kristallisation Beispiel 2
für den Erfolg der Abtrennung lediglich der Tempe- 55is readily soluble. The sulfonate is isolated at 5 ° yield: 64.2 kg of C 4 F 9 SO 3 - K + , which then corresponds to 96% as a result of subsequent crystallization at lower levels of theory; Solubility product for CaF 2 = 3.4 · temperatures or by evaporation of the solution 10 "» (18 ° C).
by means of. Since the mother liquor can be used again and again, example 2 is in the case of crystallization
for the success of the separation only the temperature 55
raturkoeffizient der Löslichkeit des Sulfonats von Be- Kaliumtrifluormethansulfonat
dcutung, der hinreichend groß sein muß, ohne daßTemperature coefficient of the solubility of the sulfonate of potassium trifluoromethanesulfonate
dcutung, which must be sufficiently large without
hierbei die Restlöslichkeit des Sulfonats bei der In einem mit Rückflußkühler, Thermometer undhere the residual solubility of the sulfonate in the one with reflux condenser, thermometer and
Kristaüisationstemperatur eine große Rolle spielt. Gaseinleitungsrohr versehenen 10-1-Kolben wurdenCrystallization temperature plays a major role. 10-1 flasks fitted with the gas inlet tube
Neben Wasser können noch folgende organische 60 10 Mol (56ü g) Kaliumhydroxid und 5 Mol (280 g)In addition to water, the following organic 60 10 mol (56 g) potassium hydroxide and 5 mol (280 g)
Lösungsmittel — im Gemisch mit Wasser — für das Calciumoxid sowie 41 destilliertes Wasser vorgelegtSolvent - mixed with water - for the calcium oxide and 41 distilled water
erfindungsgemäße Verfahren eingesetzt werden: Me- und 9,2 Mol (1400 g) TrifluormethansulfonylfluoridProcesses according to the invention are used: Me and 9.2 mol (1400 g) of trifluoromethanesulfonyl fluoride
thanol, Äthanol, Dimethylformamid oder Dimethyl- mit einer solchen Geschwindigkeit eingeleitet, daß inEthanol, ethanol, dimethylformamide or dimethyl introduced at such a rate that in
sulfoxid. dem an den Rückflußkühler anschließenden Trocken-sulfoxide. the dry condenser connected to the reflux condenser
Das erfindungsgemäße Verfahren liefert auch in 65 eiskühler kein Rückfluß zu beobachten War. DasThe process according to the invention yields no reflux even in an ice cooler. The
jenen Fällen, in denen schwerer lösliche Sulfonate vor- Reaktionsgemisch erwärmte sich auf 60°C und wurdethose cases where sparingly soluble sulfonates pre- reaction mixture warmed to 60 ° C and became
liegen, zufriedenstellende Ergebnisse, insofern, als nach Beendigung der Reaktion eine halbe Stunde beiare satisfactory results in that they are half an hour after the end of the reaction
durch Übergang von wäßrigen auf wäßrig-organische 900C nachgerührt. Nach dem Abkühlen auf Zimmer-stirred by the transition from the aqueous to aqueous-organic 90 0 C. After cooling down to room
5 65 6
temperatur wurde das ausgefallene Calciumfluorid 600C im Vakuum getrocknet Ausbeute 291 g C8F17-temperature, the precipitated calcium fluoride was dried at 60 ° C. in vacuo Yield 291 g of C 8 F 17 -
über eine Nutsche filtriert und das klare Filtrat am SO3K, das entspricht 91 % der Theorie.Filtered through a suction filter and the clear filtrate on SO 3 K, which corresponds to 91% of theory.
Rotationsverdampfer eingeengt und im Vakuum ge- Analyse:Rotary evaporator concentrated and in vacuo. Analysis:
5 0,008 %> anorganisches Fluorid, 5 0.008%> inorganic fluoride,
Gehalt an anorganischem Fluorid 0,005 % F' " 0,01 % Calcium,Inorganic fluoride content 0.005% F '"0.01% calcium,
Gehalt an Calcium 0,05% LösHchkeitsprodukt für CaF. = 3,8 · 10-« (20° C).Calcium content 0.05% solubility product for CaF. = 3.8 x 10- «(20 ° C).
Gehalt an KaliumPotassium content
gefunden 20,8% Beispiel 4found 20.8% Example 4
berechnet 20,8% to _._ , , _ ,,calculated 20.8% to _._,, _ ,,
'° Tnathylammoniumperfluoroctansulfonat '° Ethylammonium perfluorooctanesulfonate
Αμ^^Λ^Ϊ',μ: entspricht l04gC8F17SOiF96%ig(0)2MollOO%ig),5,85gCaOΑμ ^^ Λ ^ Ϊ ', μ : corresponds to l04gC 8 F 17 SO i F96% ig (0 ) 2MollOO% ig), 5.85gCaO
α Z°J? ?r± _^ 1^, ES Losl'chkeitspro- (01 Mo, 100 %iges Cll0) sowie 800 ml Wasser wurden α Z ° J? ? r ± _ ^ 1 ^, ES Losl'chkeitspro- (01 Mo , 100% Cll0) and 800 ml of water were
dukt für Cafr2 - 3,4 -10 "(18 C). in einem Reaktionsgefäß vorgelegt und unter Rührenproduct for Cafr 2 - 3.4 -10 "(18 C). placed in a reaction vessel and stirred
Beispiel 3 15 20,2 (0,2 Mol) Triäthylamin bei 25° C zugetropft NachExample 3 15 20.2 (0.2 mol) of triethylamine added dropwise at 25 ° C
„ .. _ ,. dem Aufheizen auf 700C wurde noch 1 Stunde nach-".. _,. the heating to 70 0 C was still 1 hour after
Kahumperfluoroctansulfonat 8srQbn md heißfiltriert. Das Filtrat ^fc anschUe-Kahumperfluorooctansulfonat 8srQbn md hot-filtered . The filtrate ^ fc
Zu einer Mischung, bestehend aus 39,6 g (0,6 Mol ßend etwa auf die Hälfte seines Volumens eingeengtTo a mixture consisting of 39.6 g (0.6 mol ßend concentrated to about half of its volume
100%ige KOH) Kaliumhydroxid, 18,7 g (0,3 Mol und nach dem Abkühlen auf 15°C vom ausgeschie-100% KOH) potassium hydroxide, 18.7 g (0.3 mol and after cooling to 15 ° C from the precipitated
100%iges CaO) Calciumoxid, 500ml Äthylalkohol ao denen [C8F1 ,SO3J-I(CjHs)3NH]+ abfiltriert Das Ge-100% CaO) calcium oxide, 500ml ethyl alcohol ao which [C 8 F 1 , SO 3 JI (CjHs) 3 NH] + filtered off.
und 500 ml destilliertes Wasser wurden bei 70° C unter wicht des Filterkuchens betrug nach dem Trocknenand 500 ml of distilled water were added at 70 ° C under weight of the filter cake after drying
Rühren312 g(0,6 Mol 100%iges C8F17SOjF) Perfluor- bei 6O0C im Vakuum 104 g, das entspricht einer Aus-Stirring 312 g (0.6 mol of 100% C 8 F 17 SOjF) perfluorine at 6O 0 C in a vacuum of 104 g, which corresponds to an
octansulfonylfluorid zugetropft. Am Ende der Reak- beute von 87 % der Theorie,octanesulfonyl fluoride was added dropwise. At the end of the reac- yield of 87% of theory,
tion zeigte der pH den Wert 7,0. Das Reaktions- Analysen:tion, the pH showed a value of 7.0. The reaction analysis:
gemisch wird bei 700C über eine Glasfritte vom aus- a5 0>01 ./o anorganisches Fluorid,The mixture is made from a 5 0> 01 at 70 0 C via a glass frit. / o inorganic fluoride,
gefallenen CaFt abfiltnert und auf die Hälfte semes O 08 %> Calciumfallen CaF t filtered off and half of the semes O 08%> calcium
Volumens destillativ eingeengt. Der in der Kälte aus- ' 'Concentrated in volume by distillation. Who out in the cold ''
gefallene Niederschlag wird abgenutscht und bei Löslichkeitsprodukt für CaF2 = 3,4 · 1O-11 (18° C).Any precipitate is filtered off with suction and when the solubility product for CaF 2 = 3.4 · 10 -11 (18 ° C.).
Claims (1)
steht, durch alkalische Hydrolyse dir entsprechenden Beispielhaft sollen vor allem die erfindungsgemäßThe present invention relates to pure perfluoroalkanesulfonates and the previous claim is a process for the production of practiced and described methods of preparation of practically fluoride-free perfiuoralkanes and processes (cf. for example Schröder, sulfonates, starting from perfluoroalkanesulfonic acids Gä η swei η and Brauer, Z. anorg. General Chem. RfSO 3 H, where Rf for a straight-chain or branched perfluoroalkane radical with 1 to 10 carbon atoms is clearly superior in economic terms, both in terms of technology and branching,
stands, by means of alkaline hydrolysis corresponding to the example are above all those according to the invention
alkansulfonsaurer Salze durch alkalische Hydrolyse Das erfindungsgemäße Verfahren soll nun in einerIn contrast to perfluorocarboxylic acid fluorides, inorganic fluorides formed by hydrolysis form a perfluoroalkanesulfonic acid fluoride that is slightly soluble in water, which is largely stable and can only be saponified as a solubility product of hydrolysis by using alkaline solvents, since an acidic hydrolysis also has a maximum of 10 ~ e . For this are z. B. lysis not too full even at higher temperatures. 50 Calcium, strontium, barium, magnesium, lead. Stable conversion leads (T. Gramstad and preferably calcium is used. Um das Ein-RN H aszel di ne, J, Chem. Soc. 1956, 173). To prevent dragging additional anions, accordingly, the production takes place peifluor- preferably oxides or hydroxides are used,
alkanesulfonic acid salts by alkaline hydrolysis The inventive method should now be in one
Reinigung und Isolierung des Sulfonats mit organischen Lösungsmitteln, beispielsweise Aceton oder 60the perfluoroalkanesulfonyl fluoride to the corresponding particularly preferred form using the sulfonates and inorganic fluoride. The re-calcium oxide or calcium hydroxide in more detail contains inevitably 50 mol% to be refined. The reaction can be schematically inorganic fluoride and must then be represented as follows:
Purification and isolation of the sulfonate with organic solvents, for example acetone or 60
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19732319078 DE2319078C3 (en) | 1973-04-16 | Process for the production of practically fluoride-free perfluoroalkane sulfonates | |
US454875A US3919295A (en) | 1973-04-16 | 1974-03-26 | Preparation of inorganic fluoride-free perfluoroalkane sulphonates |
FR7411159A FR2225420B1 (en) | 1973-04-16 | 1974-03-29 | |
JP49040044A JPS505325A (en) | 1973-04-16 | 1974-04-10 | |
IT50330/74A IT1004222B (en) | 1973-04-16 | 1974-04-11 | PROCEDURE FOR PRODUCING PERLUORO ALCAN SULPHONATES FROM FLUORIDE |
NL7405112A NL7405112A (en) | 1973-04-16 | 1974-04-16 | |
GB1643374A GB1432533A (en) | 1973-04-16 | 1974-04-16 | Preparation of inorganic fluoride-free perfluoroalkane sulphonates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19732319078 DE2319078C3 (en) | 1973-04-16 | Process for the production of practically fluoride-free perfluoroalkane sulfonates |
Publications (3)
Publication Number | Publication Date |
---|---|
DE2319078A1 DE2319078A1 (en) | 1974-10-31 |
DE2319078B2 DE2319078B2 (en) | 1976-06-24 |
DE2319078C3 true DE2319078C3 (en) | 1977-02-10 |
Family
ID=
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