CA1296355C - Process for preparing fluoroaliphatic ether-containing carbonyl fluoride compositions - Google Patents
Process for preparing fluoroaliphatic ether-containing carbonyl fluoride compositionsInfo
- Publication number
- CA1296355C CA1296355C CA000545509A CA545509A CA1296355C CA 1296355 C CA1296355 C CA 1296355C CA 000545509 A CA000545509 A CA 000545509A CA 545509 A CA545509 A CA 545509A CA 1296355 C CA1296355 C CA 1296355C
- Authority
- CA
- Canada
- Prior art keywords
- fluoride
- fluorinated
- bromide
- iodide
- potassium
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/175—Saturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
- C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
Abstract
PROCESS FOR PREPARING FLUOROALIPHATIC ETHER-CONTAINING
CARBONYL FLUORIDE COMPOSITIONS
Abstract Fluoroaliphatic ether-containing carbonyl fluoride compounds are prepared by reacting a fluorinated carbonyl compound with hexafluoropropylene oxide in the presence of at least one catalyst selected from potassium iodide, potassium bromide, cesium iodide, cesium bromide, rubidium iodide, and rubidium bromide.
CARBONYL FLUORIDE COMPOSITIONS
Abstract Fluoroaliphatic ether-containing carbonyl fluoride compounds are prepared by reacting a fluorinated carbonyl compound with hexafluoropropylene oxide in the presence of at least one catalyst selected from potassium iodide, potassium bromide, cesium iodide, cesium bromide, rubidium iodide, and rubidium bromide.
Description
a, l 3 i U C.~1 g~.
3 t~;
_escription PROCESS FOR PREPARING FLUOROALIPHATIC ETHER-COMTAINING
This invention relates to a process for preparing fluoroaliphatic ether-containiny carbonyl fluoride compositions.
10The preparation of perfluoroalkoxypropionic acid fluorides by reaction of hexafluoropropylene oxide, ~ O\
CF3 - CF - CF2, with perfluorocarboxylic acid fluorides in the presence of 15 various catalysts is known. U.S. Patent No. 3,250,808 IMoore et al.) discloses the reaction of hexafluoro-propylene oxide with itself, fluoroalkanoic acid fluorides, or fluoroalkanones using various catalyst systems. The catalysts employed are activated charcoal, ionizing 20 radiation, monovalent metal fluorides, particularly alkali metal fluorides, quaternary ammonium fluorides and alkali metal perfluoroalkoxides. The metal fluorides may be mixed with other alkali metal halides, e.g. lithium chloride/cesium fluoride, lithium chloride/potassium 25 fluoride, and lithium bromide~potassium fluoride. U.S.
Patent No. 3,311,658 (Warnell) discloses the use of alkali metal fluorides, quaternary ammonium fluorides, silver fluorides, and alkali metal perfluoroalkoxides as catalysts. British Patent No. 1,529,514 (duPont) discloses 30 the use of sulfonium halides and complexes thereof as catalysts for the reaction of hexafluoropropylene oxide with fluorinated carbonyl compounds. U.S. Patent No.
4,118,421 (Martini) discloses N,N,N',N'-tetrasubstituted difluorodiaminomethanes and U.S. Patent 4,035,388 (Martini) discloses tris(dialkylamino)difluorophosphoranes as catalysts for the reaction of hexafluoropropylene oxide with perfluorocarboxylic acid fluorides and perfluorocarbonyl compounds, respectively. All of these ; .
.
. ~', -,:
, 3.~
catalysts serve to promote the formation of the perfluorinated alkoxide ion which is the species which undergoes reaction with the hexafluoropropylene oxide. It 5 has also been reported [Izv. Akad. Nauk SSSR, Ser. Khim.
1891 (1983)] that the potassium halide salts potassium fluoride, potassium chloride, potassium bromide, and potassium iodide catalyze the oligomeri~ation of hexafluoropropylene oxide, the use of the potassium 10 fluoride resulting in the formation of hexafluoropropylene oxide oligomers up to the hexamer and the use of the potassium iodide resulting in the formation of mainly dimer and trimer.
This invention provides a process for preparing 15 fluoroaliphatic ether-containing carbonyl fluoride ~ comprising reacting hexafluoropropylene oxide, ~0\
CF3 - CF - CF2, with a fluorinated carbonyl compound selected from fluorinated ketone and fluorinated acyl 20 fluorides in the presence of at least one catalyst selected from potassium iodide, potassium bromide, cesium iodide, cesium bromide, rubidium iodide, and rubidium bromide.
Suitable reactive fluorinated carbonyl compounds useful in the process of the invention include those which 25 can be represented by the general formula Rl-C~R2 where Rl and R2 are independently: F; fluoroalkyl groups, 30 Rf, which are substantially perfluorinated and can be linear or branched, and which can contain H, Cl or Br atoms and can contain catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms of the skeletal chain, such hetero atoms providing stable ~inkages between fluorocarbon portions of the chain; fluorosulfonyl substituted perfluoroalkyl groups; fluorocarbonyl groups;
fluorocarbonyl substituted perfluoroalkyl groups;
alkoxycarbonyl substituted perfluoroalkyl groups; or R1 and ~ . .
~63.~.~5 R2 together with the -C- group can form a 4- to 7- membered ring; each of R1 and R2 having no more than 20 carbon 5 atoms.
A subclass of the fluorinated carbonyl compounds useful in the process of this invention can be represented by the formula 1 0 1l FCRf 'X II
where X is H, F, Cl, Br, ROC- where R is a lower alkyl group having 1 to 8 carbon atoms, FSO2-, or FC-; and R~' is a perfluoroalkylene group, having 1 to 20 carbon atoms, which is substantially perfluorinated and can be linear or branched, and which can contain one or more H, Cl or Br 20 ato~s, and can contain catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms of the skeletal chain, such hetero atoms providing stable linkages between fluorocarbon portions of the chain.
Fluorinated carbonyl compounds which can be used 25 in the process of the invention include COF2, FCOCOF, CF3COF, C2FsCOF, n-C3F~COF, i-C3F7COF, C2F50CF2COF, . C3F70C(CF3)FCOF, C3F70[C(CF3 )FCF20]3C(CF3 )FCOF, C2FsOCF2CF20CF2COF, H(CF2) 6 COF, BrCF2COF, ClCF2COF, FS02 ( CF2 ) 3 COF, CF3COCF3, HCF2COCF2H, FOCCF2cF2coF~
30 FOCCF~CF2COOCH3, CF3CQCF20C(CF3)FCOOCH3, CH3S02CF2CF2COCF~, CF3CFHCOF, C3 F, OC ( CF2 Cl)FCOF, C7F1sCOF, 7oc(cF2cl)FcF2oc(cF2cl)FcOF~ (C2Fs) 2 WCF2CF2CF~
FOCC(CF3)FOCF2CF2COOCH3, FOCC(CF3)FOCF2CF2COOC2H5, 35 ~ -, ~ -O, and ~ =o.
The fluoroaliphatic ether-containing carbonyl fluoride compositions produced by the process of this : , .
3~
invention comprise mixtures of compounds represented by the formula S Rs CF2 O ( CFCF2 O ) p I FCOF
CFl CF3 where Rf is as defined above and p ls zero or a number up to about 10 or higher.
Representative reaction schemes illustrative of the process of the invention are shown below. In each scheme Rf is as defined above, M is K, Rb or Cs, X is bromide or iodide, and p is a number from 1 to about 10.
Scheme 1 COF + p+ 1 C F C F--C F 2 --> R ~ C F 2 ( C FC F2 ) p Scheme 2 / \ MX ICF3 CF3 (R~) 2 CO + p~l CF3 CF-CF2 --> ( Rf ) 2 CFO ( CFCF2 O ) p CFCOF
The process of this invention is preferably carried out in a polar organic solvent. Suitable solvents 25 include aliphatic ethers such as diglyme, triglyme, and tetraglyme, with diglyme (diethylene glycol dimethyl ether) being generally more preferred, although the higher boiling point solvents, e.g., tetraglyme, are more preferred where recovery of low boiling point fluoroaliphatic ether-containing carbonyl fluoride compounds from the reaction product is required. Other solvents such as acetone or acetonitrile may also be employed. Reaction temperatures can vary widely, e.g., from about -80 to 100C, preferably -30 to 60C. Reaction time is generally from several minutes to about 50 hours depending on the scale of the reaction, with larger scale reactions requiring longer times. The reaction is generally carried out at atmospheric pressure, although higher pressure can : ~
, ~ '' ~ .
: :
~ .
::
- ~ ~J~ 3~
be used, and re~uires no special equipment. To perform the reaction, the solvent and the fluorinated carbonyl compounds are charged to the reaction vessel and the 5 catalyst is then added followed by addition of the hexafluoropropylene oxide, or the solvent and catalyst are charged to the reaction vessel and the fluorinated carbonyl compound is added and then the hexafluoropropylene oxide is added. Generally, processes for producing carbonyl 10 fluoride compositions must be carried out under scrupulously anhydrous conditions, i.e., less than 100 ppm water, to prevent hydrolysis of the transitory intermediate perfluoroalkoxide, RfCF2OCFCF2O-M+ which would result in 15 the formation of RfCF2OCFCOOH. Surprisingly, the process of the present invention need only be carried out under substantially anhydrous conditions, i.e., less than 2000 ppm, more preferably less than 1000 ppm water.
The preferred catalysts are potassium iodide and potassium bromide. Potassium chloride alone does not catalyze the reaction, although it will give a small yield of the desired products when a crown ether such as 18-crown-6 is employed as a co-catalyst.
The fluoroaliphatic ether-containing carbonyl fluoride compositions resulting from the reaction can be recovered from the reaction product mixture by phase separation followed by distillation.
The yields of the fluoroaliphatic ether-containing carbonyI fluoride composition from the reaction employing the catalysts of this invention are high, e.g., generally 50% or more based on the fluorinated carbonyl compound when the catalyst is potassium iodide or bromide, such yields frequently superior to those obtained with more commonly utilized catalysts such as cesium fluoride. The composition of the recovered fluoroaliphatic ether-containing carbonyl fluoride composition is substantially the same as that obtained by using cesium .. ~ '.
3~;5 fluoride as the catalyst, although when potassium bromide is used as the catalyst there is a small amount of bromine--containing material in the final product.
In admixture with the fluoroaliphatic monoether compounds (Scheme 1, where p is 1), there are fluoroaliphatic polyether compounds which are formed by the addition of more units of hexafluoropropylene oxide, e.g., where p is 2 to 10 or higher. Under the appropriate 10 conditions, e.g. when a higher molar ratio of hexafluoropropylene oxide to fluorinated carbonyl reactant is used, the polyether materials may become the major products.
The concentration of the catalyst used is, 15 functionally stated, a catalytic amount, and this amount can be empirically determined. Generally that amount need not exceed about 12 mole percent based on the fluorinated carbonyl compound when potassium iodide is the catalyst.
With potassium bromide, it is occasionally necessary to use 20 somewhat larger amounts of catalyst ranging up to 100 mole percent based on the fluorinated carbonyl compound. The use of higher amounts of catalyst than that determined empirically is not detrimental to the reaction but offers no particular advantages.
The fluoroaliphatic ether-containing carbonyl fluorides produced by the process of this invention are useful intermediates for the preparation of many derivatives, e.g., carboxylic acids and their salts, esters, amides, alcohols, acrylates, vinyl ethers, 30 polymers, etc., as described in U.S. Patents No. 3,250,808 (Moore et al.) and No. 3,699,156 (Holland et al.). These derivatives have utility for various applications, such as surfactants, lubricants, heat transfer and cooling fluids, hydraulic fluids and vapor phase heating.
To further illustrate this invention, the followinq nonlimiting examples are provided. In these examples, amounts are in weight percent unless otherwise indicated. All products had physical and analytical .
~ 3t~
properties which were fully consistent with their structure and agreed with the data from products prepared by an alternate route. Gas chromatographic (GC) analysis of the 5 reaction products, after conversion to the methyl esters, using a 3 meter OV101 column, gave baseline separation of the starting materials and the fluoroaliphatic ether products. Infrared (IR) spectral analysis of the products showed the characteristic carbonyl fluoride s~retch at 5.22 10 microns. Fluorine nuclear magnetic resonance ( F NMR) analysis was occasionally complicated by the presence of isomers and non-carbonyl-containing impurities present in the original starting acid fluorides, as well as some overlap in the 75-85 ppm range, but showed the 15 characteristic -COF fluorine at ~26 ppm downfield from the internal CFCl3 standard. Mass spectral (MS) analysis was also carried out in some cases. Additional confirmation of the aliphatic ether-containing carbonyl fluoride products was obtained by conversion to the corresponding 20 perfluorinated vinyl ether using standard procedures as described in U.S. Patent No. 3,250,808 (Moore et al.) Yields were based on GC area percentages corrected for non-hexafluoropropylene oxide derived materials.
Example 1 Potassium iodide (3.07 g, 0.018 mole) which had been vacuum dried was added to diglyme ~42 g, distilled from scdium benzophenone ketyl) contained in a 250 ml, 3-necked, round bottom flask equipped with a Dry 3Q IceTM-acetone condenser, an overhead stirrer, and a gas inlet, and cooled to -20C. Tetrafluorosuccinyl fluoride, FCOCF2 CF2 COF ( 40 g of 75% purity, 0.15 mole), was added and the mixture stirred for 45 minutes. Hexafluoropropylene oxide (50 g of 80% purity, 0.30 mole) was added over 45 minutes. The reaction mixture was separated. The lower - fluorochemical phase contained: 35% FOC(CF2)30CF(CF3 )COF
and 49% FOCCF(CF3 )O(CF2 )40CF(CF3 )COF, a yield of 95% based on tetrafluorosuccinyl fluoride. The remainder (16%) of ~ ~¢3~ rilrj the fluorochemical phase was starting material and a small amount of hexafluoropropylene oxlde oligomers.
Example Z
Potassium iodide (1.7 g, 0.01 mole) and diglyme (50 g) were combined as in Example 1 and cooled to -20C.
Trifluoroacetyl fluoride, CF3COF (10 g, 0.086 mole), was added as a gas over a period of about 10 minutes with 10 stirring and the mixture was further stirred for 20 minutes. Hexafluoropropylene oxide (17.9 g of 80% purity, 0.086 mole) was added and the mixture stirred until reflux from the Dry Ice condenser had ceased. rrhe fluorochemical product layer was separated and reacted with methanol-BF3 15 at 0-5C for 10 minutes to convert the volatile acyl fluorides to the corresponding methyl ester. The product contained about 100% fluoroaliphatic ether-containing methyl ester compounds, C2FsO~CF(CF3)CF2O]XCF(CF3)CO2CH3, with the product distribution being x=0 (49%), x-1 (45%) 20 and x=2 (6%). Yield of the product was 56% based on CF3COF. Trace amounts of hexafluoropropylene oxide oligomers were also formed.
Example 3 Potassium iodide (4.5 g, 0.027 mole) and diglyme (60 g) were combined as in Example 1 and cooled to -20C.
Heptafluorobutyryl fluoride, C3F7COF (70.9 g of 43% purity, 0.14 mole) was added and the mixture stirred.
Hexafluoropropylene oxide (58.5 g of 80% purity, 0.28 mole) was added over 30 minutes. The reaction mixture was allowed to warm to about 25C over a five-hour period and the resulting product was found to contain 91%
fluoroaliphatic ether-containing carbonyl fluoride compounds, C4 FgO[CF(CF3)CF2O]XCF(CF3)COF, with the product distribution being x=0 (23%), x=1 (54%) and x-2 (23%), in a nearly quantitative yield based on C3F7COF. Nine percent of the fluorochemical product was hexafluoropropylene oxide oligomers.
.
3~S
Example 4 ~sing the procedure of Example 1, potassium 5 iodide (2.55 g, 0.015 mole), diglyme (80 g) and perfluoro(diethylaminopropionyl) fluoride, (C2F5)2NCF2CF2COF, (100 g of 51% purity, 0.129 mole) were combined and stirred at 0C for 45 minutes.
Hexafluoropropylene oxide (28 g of 80% purity, 0.135 mole) 10 was added and the mixture stirred for 4 hours and then slowly allowed to warm to about 25C over a 2-hour period.
The resulting two-phase reaction mixture was separated and the lower fluorochemical phase analyzed and found to contain 59% fluoroaliphatic ether-containing carbonyl-15 fluoride compounds,(C2F5)2N(CF2)30[CF(CF3)CF2O]xCF(CF3)COF, with the product distribution being x~0 (80%) and x~1 (20~), in a yield of 76% based on starting acyl fluoride. The remainder of the fluorochemical product was starting material and 20 hexafluoropropylene oxide oligomers.
Example 5 Potassium iodide (1.2 g, 0.007 mole) and diglyme (50 g) were combined as in Example 1 and cooled to -20C.
25 An extra condenser was placed on top of the first Dry Ice condenser and both were filled with Dry Ice-diethyl ether.
Carbonyl fluoride, COF2 (5.0 g, 0.076 mole) was added as a gas. Hexafluoropropylene oxide (25.1 g, 0.15 mole) was added over a fifteen minute period. The resulting mixture 30 was stirred for two hours and the lower fluorochemical phase was then separated. For ease of analysis due to the volatility of the acyl fluoride, the product was converted to the methyl ester as in Example 2. GC-MS an~ 19 F NMR
analysis of the reaction mixture showed the expected 35 fluoroaliphatic ether-containing methyl ester compounds, 3 [CFtCF3)CF2O]xCF(CF3)co2cH3~where x was 1 to 5, and an equal amount of hexa~luoropropylene oxide oligomers.
~2,~
~ ple 6 Potassium iodide (1.20 g, 0.007 mole) and diglyme (50 g) were combined as in Example 1 and cooled to -20C.
5 Hexafluoroacetone (8.0 g, 0.048 mole) was condensed into the mixture and the suspension stirred for 25 minutes.
Hexafluoropropylene oxide ~20.0 y of 80% purity, 0.096 mole) was added over a period of 20 minutes and the resulting mixture stirred for two hours while slowly 10 warming to about 25C. The lower fluorochemical phase was separated to give 21.7 g of a mixture of fluoroaliphatic ether-containing carbonyl fluoride compounds, (CF3)2CFO[CF(CF3)CF2O]xCF(CF3)COF,where x=0 to 3 and hexafluoropropylene oxide oligomers in a 4:1 mole ratio.
Example 7 Diglyme (92.5 kg) (Ansul E-141, Ansul Co.; water content 640 ppm) was charged into a 189 L refrigerated stainless steel reactor followed by the addition of 20 potassium iodide (3.9 kg, 23.5 mole) (Mallinckrodt). The batch was cooled to -12C and C3 F~COF (77 kg of 51% purity, 181 mole) was added rapidly. The mixture was agitated for two hours at -12C. Hexafluoropropylene oxide (77 kg, 464.9 mole) was subse~uently added such that the 25 temperature of the reaction did not exceed -12C. After the addition of the hexafluoropropylene oxide was complete, the reactor was held for one hour at -18 to -12C. The batch was then heated for 1 hour to 52C to remove the lower boiling impurities. After cooling to 21C over a 2 hour period, the bottom fluorochemical phase was separated to give 118 kg (80%) fluoroaliphatic ether-containing carbonyl fluoride compounds, C4FgO[CF(CF3)CF2O]xCF(CF3)COF,with the product distribution being x=0 (20%), x-1 (65%) and x=2 (15%), and 20% hexafluoropropylene oxide oligomers, C3F7o[cF(cF3)cF2o]xcF(cF3)coF~with the product distribution being x=0 (40%), x=1 (50%) and x=2 (10%).
The mole percent yield of fluoroaliphatic ether-containing 3~
carbonyl fluoride compounds based on C3 F7COF was 90% and based on hexafluoropropylene oxide was 82%.
Example 8 Potassium iodide (7.1g, 0.043 mole) and diglyme (94g) were combined as in Example 1. 4-(Fluorosulfonyl)-hexafluorobutyryl fluoride, FO25(CF2)3COF, (173g of 58%
purity, 0.358 mole) was added at 25C and the contents 10 stirred for 30 minutes and -then cooled to 0C.
Hexafluoropropylene oxide (151g, 0.910 mole) was added over four hours with the bulk (120g) added within the first hour. After the reaction was complete, the phases were ~eparated and the lower fluorochemical phase (290g) was 15 analyzed and found to contain 64~ fluoroaliphatic ether-containing carbonyl fluoride compounds, FO2S(CF2)4O~CF(CF3)CF2O]XCF(CF3)CoF~ with the product distribution being x=0 (17%), x=1 (72%) and x=2 (11%), in a yield of 89% based on starting acid fluoride. The 20 remainder of the fluorochemical phase (36%) was starting material.
The various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this 25 invention and this invention should not be restricted to that set forth herein for illustrative purposes.
. .
.
3 t~;
_escription PROCESS FOR PREPARING FLUOROALIPHATIC ETHER-COMTAINING
This invention relates to a process for preparing fluoroaliphatic ether-containiny carbonyl fluoride compositions.
10The preparation of perfluoroalkoxypropionic acid fluorides by reaction of hexafluoropropylene oxide, ~ O\
CF3 - CF - CF2, with perfluorocarboxylic acid fluorides in the presence of 15 various catalysts is known. U.S. Patent No. 3,250,808 IMoore et al.) discloses the reaction of hexafluoro-propylene oxide with itself, fluoroalkanoic acid fluorides, or fluoroalkanones using various catalyst systems. The catalysts employed are activated charcoal, ionizing 20 radiation, monovalent metal fluorides, particularly alkali metal fluorides, quaternary ammonium fluorides and alkali metal perfluoroalkoxides. The metal fluorides may be mixed with other alkali metal halides, e.g. lithium chloride/cesium fluoride, lithium chloride/potassium 25 fluoride, and lithium bromide~potassium fluoride. U.S.
Patent No. 3,311,658 (Warnell) discloses the use of alkali metal fluorides, quaternary ammonium fluorides, silver fluorides, and alkali metal perfluoroalkoxides as catalysts. British Patent No. 1,529,514 (duPont) discloses 30 the use of sulfonium halides and complexes thereof as catalysts for the reaction of hexafluoropropylene oxide with fluorinated carbonyl compounds. U.S. Patent No.
4,118,421 (Martini) discloses N,N,N',N'-tetrasubstituted difluorodiaminomethanes and U.S. Patent 4,035,388 (Martini) discloses tris(dialkylamino)difluorophosphoranes as catalysts for the reaction of hexafluoropropylene oxide with perfluorocarboxylic acid fluorides and perfluorocarbonyl compounds, respectively. All of these ; .
.
. ~', -,:
, 3.~
catalysts serve to promote the formation of the perfluorinated alkoxide ion which is the species which undergoes reaction with the hexafluoropropylene oxide. It 5 has also been reported [Izv. Akad. Nauk SSSR, Ser. Khim.
1891 (1983)] that the potassium halide salts potassium fluoride, potassium chloride, potassium bromide, and potassium iodide catalyze the oligomeri~ation of hexafluoropropylene oxide, the use of the potassium 10 fluoride resulting in the formation of hexafluoropropylene oxide oligomers up to the hexamer and the use of the potassium iodide resulting in the formation of mainly dimer and trimer.
This invention provides a process for preparing 15 fluoroaliphatic ether-containing carbonyl fluoride ~ comprising reacting hexafluoropropylene oxide, ~0\
CF3 - CF - CF2, with a fluorinated carbonyl compound selected from fluorinated ketone and fluorinated acyl 20 fluorides in the presence of at least one catalyst selected from potassium iodide, potassium bromide, cesium iodide, cesium bromide, rubidium iodide, and rubidium bromide.
Suitable reactive fluorinated carbonyl compounds useful in the process of the invention include those which 25 can be represented by the general formula Rl-C~R2 where Rl and R2 are independently: F; fluoroalkyl groups, 30 Rf, which are substantially perfluorinated and can be linear or branched, and which can contain H, Cl or Br atoms and can contain catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms of the skeletal chain, such hetero atoms providing stable ~inkages between fluorocarbon portions of the chain; fluorosulfonyl substituted perfluoroalkyl groups; fluorocarbonyl groups;
fluorocarbonyl substituted perfluoroalkyl groups;
alkoxycarbonyl substituted perfluoroalkyl groups; or R1 and ~ . .
~63.~.~5 R2 together with the -C- group can form a 4- to 7- membered ring; each of R1 and R2 having no more than 20 carbon 5 atoms.
A subclass of the fluorinated carbonyl compounds useful in the process of this invention can be represented by the formula 1 0 1l FCRf 'X II
where X is H, F, Cl, Br, ROC- where R is a lower alkyl group having 1 to 8 carbon atoms, FSO2-, or FC-; and R~' is a perfluoroalkylene group, having 1 to 20 carbon atoms, which is substantially perfluorinated and can be linear or branched, and which can contain one or more H, Cl or Br 20 ato~s, and can contain catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms of the skeletal chain, such hetero atoms providing stable linkages between fluorocarbon portions of the chain.
Fluorinated carbonyl compounds which can be used 25 in the process of the invention include COF2, FCOCOF, CF3COF, C2FsCOF, n-C3F~COF, i-C3F7COF, C2F50CF2COF, . C3F70C(CF3)FCOF, C3F70[C(CF3 )FCF20]3C(CF3 )FCOF, C2FsOCF2CF20CF2COF, H(CF2) 6 COF, BrCF2COF, ClCF2COF, FS02 ( CF2 ) 3 COF, CF3COCF3, HCF2COCF2H, FOCCF2cF2coF~
30 FOCCF~CF2COOCH3, CF3CQCF20C(CF3)FCOOCH3, CH3S02CF2CF2COCF~, CF3CFHCOF, C3 F, OC ( CF2 Cl)FCOF, C7F1sCOF, 7oc(cF2cl)FcF2oc(cF2cl)FcOF~ (C2Fs) 2 WCF2CF2CF~
FOCC(CF3)FOCF2CF2COOCH3, FOCC(CF3)FOCF2CF2COOC2H5, 35 ~ -, ~ -O, and ~ =o.
The fluoroaliphatic ether-containing carbonyl fluoride compositions produced by the process of this : , .
3~
invention comprise mixtures of compounds represented by the formula S Rs CF2 O ( CFCF2 O ) p I FCOF
CFl CF3 where Rf is as defined above and p ls zero or a number up to about 10 or higher.
Representative reaction schemes illustrative of the process of the invention are shown below. In each scheme Rf is as defined above, M is K, Rb or Cs, X is bromide or iodide, and p is a number from 1 to about 10.
Scheme 1 COF + p+ 1 C F C F--C F 2 --> R ~ C F 2 ( C FC F2 ) p Scheme 2 / \ MX ICF3 CF3 (R~) 2 CO + p~l CF3 CF-CF2 --> ( Rf ) 2 CFO ( CFCF2 O ) p CFCOF
The process of this invention is preferably carried out in a polar organic solvent. Suitable solvents 25 include aliphatic ethers such as diglyme, triglyme, and tetraglyme, with diglyme (diethylene glycol dimethyl ether) being generally more preferred, although the higher boiling point solvents, e.g., tetraglyme, are more preferred where recovery of low boiling point fluoroaliphatic ether-containing carbonyl fluoride compounds from the reaction product is required. Other solvents such as acetone or acetonitrile may also be employed. Reaction temperatures can vary widely, e.g., from about -80 to 100C, preferably -30 to 60C. Reaction time is generally from several minutes to about 50 hours depending on the scale of the reaction, with larger scale reactions requiring longer times. The reaction is generally carried out at atmospheric pressure, although higher pressure can : ~
, ~ '' ~ .
: :
~ .
::
- ~ ~J~ 3~
be used, and re~uires no special equipment. To perform the reaction, the solvent and the fluorinated carbonyl compounds are charged to the reaction vessel and the 5 catalyst is then added followed by addition of the hexafluoropropylene oxide, or the solvent and catalyst are charged to the reaction vessel and the fluorinated carbonyl compound is added and then the hexafluoropropylene oxide is added. Generally, processes for producing carbonyl 10 fluoride compositions must be carried out under scrupulously anhydrous conditions, i.e., less than 100 ppm water, to prevent hydrolysis of the transitory intermediate perfluoroalkoxide, RfCF2OCFCF2O-M+ which would result in 15 the formation of RfCF2OCFCOOH. Surprisingly, the process of the present invention need only be carried out under substantially anhydrous conditions, i.e., less than 2000 ppm, more preferably less than 1000 ppm water.
The preferred catalysts are potassium iodide and potassium bromide. Potassium chloride alone does not catalyze the reaction, although it will give a small yield of the desired products when a crown ether such as 18-crown-6 is employed as a co-catalyst.
The fluoroaliphatic ether-containing carbonyl fluoride compositions resulting from the reaction can be recovered from the reaction product mixture by phase separation followed by distillation.
The yields of the fluoroaliphatic ether-containing carbonyI fluoride composition from the reaction employing the catalysts of this invention are high, e.g., generally 50% or more based on the fluorinated carbonyl compound when the catalyst is potassium iodide or bromide, such yields frequently superior to those obtained with more commonly utilized catalysts such as cesium fluoride. The composition of the recovered fluoroaliphatic ether-containing carbonyl fluoride composition is substantially the same as that obtained by using cesium .. ~ '.
3~;5 fluoride as the catalyst, although when potassium bromide is used as the catalyst there is a small amount of bromine--containing material in the final product.
In admixture with the fluoroaliphatic monoether compounds (Scheme 1, where p is 1), there are fluoroaliphatic polyether compounds which are formed by the addition of more units of hexafluoropropylene oxide, e.g., where p is 2 to 10 or higher. Under the appropriate 10 conditions, e.g. when a higher molar ratio of hexafluoropropylene oxide to fluorinated carbonyl reactant is used, the polyether materials may become the major products.
The concentration of the catalyst used is, 15 functionally stated, a catalytic amount, and this amount can be empirically determined. Generally that amount need not exceed about 12 mole percent based on the fluorinated carbonyl compound when potassium iodide is the catalyst.
With potassium bromide, it is occasionally necessary to use 20 somewhat larger amounts of catalyst ranging up to 100 mole percent based on the fluorinated carbonyl compound. The use of higher amounts of catalyst than that determined empirically is not detrimental to the reaction but offers no particular advantages.
The fluoroaliphatic ether-containing carbonyl fluorides produced by the process of this invention are useful intermediates for the preparation of many derivatives, e.g., carboxylic acids and their salts, esters, amides, alcohols, acrylates, vinyl ethers, 30 polymers, etc., as described in U.S. Patents No. 3,250,808 (Moore et al.) and No. 3,699,156 (Holland et al.). These derivatives have utility for various applications, such as surfactants, lubricants, heat transfer and cooling fluids, hydraulic fluids and vapor phase heating.
To further illustrate this invention, the followinq nonlimiting examples are provided. In these examples, amounts are in weight percent unless otherwise indicated. All products had physical and analytical .
~ 3t~
properties which were fully consistent with their structure and agreed with the data from products prepared by an alternate route. Gas chromatographic (GC) analysis of the 5 reaction products, after conversion to the methyl esters, using a 3 meter OV101 column, gave baseline separation of the starting materials and the fluoroaliphatic ether products. Infrared (IR) spectral analysis of the products showed the characteristic carbonyl fluoride s~retch at 5.22 10 microns. Fluorine nuclear magnetic resonance ( F NMR) analysis was occasionally complicated by the presence of isomers and non-carbonyl-containing impurities present in the original starting acid fluorides, as well as some overlap in the 75-85 ppm range, but showed the 15 characteristic -COF fluorine at ~26 ppm downfield from the internal CFCl3 standard. Mass spectral (MS) analysis was also carried out in some cases. Additional confirmation of the aliphatic ether-containing carbonyl fluoride products was obtained by conversion to the corresponding 20 perfluorinated vinyl ether using standard procedures as described in U.S. Patent No. 3,250,808 (Moore et al.) Yields were based on GC area percentages corrected for non-hexafluoropropylene oxide derived materials.
Example 1 Potassium iodide (3.07 g, 0.018 mole) which had been vacuum dried was added to diglyme ~42 g, distilled from scdium benzophenone ketyl) contained in a 250 ml, 3-necked, round bottom flask equipped with a Dry 3Q IceTM-acetone condenser, an overhead stirrer, and a gas inlet, and cooled to -20C. Tetrafluorosuccinyl fluoride, FCOCF2 CF2 COF ( 40 g of 75% purity, 0.15 mole), was added and the mixture stirred for 45 minutes. Hexafluoropropylene oxide (50 g of 80% purity, 0.30 mole) was added over 45 minutes. The reaction mixture was separated. The lower - fluorochemical phase contained: 35% FOC(CF2)30CF(CF3 )COF
and 49% FOCCF(CF3 )O(CF2 )40CF(CF3 )COF, a yield of 95% based on tetrafluorosuccinyl fluoride. The remainder (16%) of ~ ~¢3~ rilrj the fluorochemical phase was starting material and a small amount of hexafluoropropylene oxlde oligomers.
Example Z
Potassium iodide (1.7 g, 0.01 mole) and diglyme (50 g) were combined as in Example 1 and cooled to -20C.
Trifluoroacetyl fluoride, CF3COF (10 g, 0.086 mole), was added as a gas over a period of about 10 minutes with 10 stirring and the mixture was further stirred for 20 minutes. Hexafluoropropylene oxide (17.9 g of 80% purity, 0.086 mole) was added and the mixture stirred until reflux from the Dry Ice condenser had ceased. rrhe fluorochemical product layer was separated and reacted with methanol-BF3 15 at 0-5C for 10 minutes to convert the volatile acyl fluorides to the corresponding methyl ester. The product contained about 100% fluoroaliphatic ether-containing methyl ester compounds, C2FsO~CF(CF3)CF2O]XCF(CF3)CO2CH3, with the product distribution being x=0 (49%), x-1 (45%) 20 and x=2 (6%). Yield of the product was 56% based on CF3COF. Trace amounts of hexafluoropropylene oxide oligomers were also formed.
Example 3 Potassium iodide (4.5 g, 0.027 mole) and diglyme (60 g) were combined as in Example 1 and cooled to -20C.
Heptafluorobutyryl fluoride, C3F7COF (70.9 g of 43% purity, 0.14 mole) was added and the mixture stirred.
Hexafluoropropylene oxide (58.5 g of 80% purity, 0.28 mole) was added over 30 minutes. The reaction mixture was allowed to warm to about 25C over a five-hour period and the resulting product was found to contain 91%
fluoroaliphatic ether-containing carbonyl fluoride compounds, C4 FgO[CF(CF3)CF2O]XCF(CF3)COF, with the product distribution being x=0 (23%), x=1 (54%) and x-2 (23%), in a nearly quantitative yield based on C3F7COF. Nine percent of the fluorochemical product was hexafluoropropylene oxide oligomers.
.
3~S
Example 4 ~sing the procedure of Example 1, potassium 5 iodide (2.55 g, 0.015 mole), diglyme (80 g) and perfluoro(diethylaminopropionyl) fluoride, (C2F5)2NCF2CF2COF, (100 g of 51% purity, 0.129 mole) were combined and stirred at 0C for 45 minutes.
Hexafluoropropylene oxide (28 g of 80% purity, 0.135 mole) 10 was added and the mixture stirred for 4 hours and then slowly allowed to warm to about 25C over a 2-hour period.
The resulting two-phase reaction mixture was separated and the lower fluorochemical phase analyzed and found to contain 59% fluoroaliphatic ether-containing carbonyl-15 fluoride compounds,(C2F5)2N(CF2)30[CF(CF3)CF2O]xCF(CF3)COF, with the product distribution being x~0 (80%) and x~1 (20~), in a yield of 76% based on starting acyl fluoride. The remainder of the fluorochemical product was starting material and 20 hexafluoropropylene oxide oligomers.
Example 5 Potassium iodide (1.2 g, 0.007 mole) and diglyme (50 g) were combined as in Example 1 and cooled to -20C.
25 An extra condenser was placed on top of the first Dry Ice condenser and both were filled with Dry Ice-diethyl ether.
Carbonyl fluoride, COF2 (5.0 g, 0.076 mole) was added as a gas. Hexafluoropropylene oxide (25.1 g, 0.15 mole) was added over a fifteen minute period. The resulting mixture 30 was stirred for two hours and the lower fluorochemical phase was then separated. For ease of analysis due to the volatility of the acyl fluoride, the product was converted to the methyl ester as in Example 2. GC-MS an~ 19 F NMR
analysis of the reaction mixture showed the expected 35 fluoroaliphatic ether-containing methyl ester compounds, 3 [CFtCF3)CF2O]xCF(CF3)co2cH3~where x was 1 to 5, and an equal amount of hexa~luoropropylene oxide oligomers.
~2,~
~ ple 6 Potassium iodide (1.20 g, 0.007 mole) and diglyme (50 g) were combined as in Example 1 and cooled to -20C.
5 Hexafluoroacetone (8.0 g, 0.048 mole) was condensed into the mixture and the suspension stirred for 25 minutes.
Hexafluoropropylene oxide ~20.0 y of 80% purity, 0.096 mole) was added over a period of 20 minutes and the resulting mixture stirred for two hours while slowly 10 warming to about 25C. The lower fluorochemical phase was separated to give 21.7 g of a mixture of fluoroaliphatic ether-containing carbonyl fluoride compounds, (CF3)2CFO[CF(CF3)CF2O]xCF(CF3)COF,where x=0 to 3 and hexafluoropropylene oxide oligomers in a 4:1 mole ratio.
Example 7 Diglyme (92.5 kg) (Ansul E-141, Ansul Co.; water content 640 ppm) was charged into a 189 L refrigerated stainless steel reactor followed by the addition of 20 potassium iodide (3.9 kg, 23.5 mole) (Mallinckrodt). The batch was cooled to -12C and C3 F~COF (77 kg of 51% purity, 181 mole) was added rapidly. The mixture was agitated for two hours at -12C. Hexafluoropropylene oxide (77 kg, 464.9 mole) was subse~uently added such that the 25 temperature of the reaction did not exceed -12C. After the addition of the hexafluoropropylene oxide was complete, the reactor was held for one hour at -18 to -12C. The batch was then heated for 1 hour to 52C to remove the lower boiling impurities. After cooling to 21C over a 2 hour period, the bottom fluorochemical phase was separated to give 118 kg (80%) fluoroaliphatic ether-containing carbonyl fluoride compounds, C4FgO[CF(CF3)CF2O]xCF(CF3)COF,with the product distribution being x=0 (20%), x-1 (65%) and x=2 (15%), and 20% hexafluoropropylene oxide oligomers, C3F7o[cF(cF3)cF2o]xcF(cF3)coF~with the product distribution being x=0 (40%), x=1 (50%) and x=2 (10%).
The mole percent yield of fluoroaliphatic ether-containing 3~
carbonyl fluoride compounds based on C3 F7COF was 90% and based on hexafluoropropylene oxide was 82%.
Example 8 Potassium iodide (7.1g, 0.043 mole) and diglyme (94g) were combined as in Example 1. 4-(Fluorosulfonyl)-hexafluorobutyryl fluoride, FO25(CF2)3COF, (173g of 58%
purity, 0.358 mole) was added at 25C and the contents 10 stirred for 30 minutes and -then cooled to 0C.
Hexafluoropropylene oxide (151g, 0.910 mole) was added over four hours with the bulk (120g) added within the first hour. After the reaction was complete, the phases were ~eparated and the lower fluorochemical phase (290g) was 15 analyzed and found to contain 64~ fluoroaliphatic ether-containing carbonyl fluoride compounds, FO2S(CF2)4O~CF(CF3)CF2O]XCF(CF3)CoF~ with the product distribution being x=0 (17%), x=1 (72%) and x=2 (11%), in a yield of 89% based on starting acid fluoride. The 20 remainder of the fluorochemical phase (36%) was starting material.
The various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of this 25 invention and this invention should not be restricted to that set forth herein for illustrative purposes.
. .
.
Claims (10)
1. A process for preparing fluoroaliphatic ether-containing carbonyl fluoride compounds comprising reacting hexafluoropropylene oxide with a fluorinated carbonyl compound selected from fluorinated ketone and fluorinated acyl fluorides in the presence of at least one catalyst selected from potassium iodide, potassium bromide, cesium iodide, cesium bromide, rubidium iodide, and rubidium bromide.
2. The process of claim 1 wherein said reaction is conducted in a polar organic solvent.
3. The process of claim 1 wherein said process is carried out under substantially anhydrous conditions.
4. The process of claim 1 wherein said reaction is conducted at a temperature of about -80°C to 100°C.
5. The process of claim 1 wherein said process further comprises recovering said fluoroaliphatic ether-containing carbonyl fluoride compounds by phase separation followed by distillation.
6. The process of claim 1 wherein said fluorinated carbonyl compound is represented by the formula I
where R1 and R2 are independently F; fluoroalkyl groups, Rf, which are substantially perfluorinated and can be linear or branched, and which can contain H, Cl or Br atoms and can contain catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms of the skeletal chain, such hetero atoms providing stable linkages between fluorocarbon portions of the chain; fluorosulfonyl substituted perfluoroalkyl groups; fluorocarbonyl groups;
fluorocarbonyl substituted perfluoroalkyl groups;
alkoxycarbonyl substituted perfluoroalkyl groups; or the R1 and R2 together with the -?- group can form a 4- to 7-membered ring; each of R1 and R2 having no more than 20 carbon atoms.
where R1 and R2 are independently F; fluoroalkyl groups, Rf, which are substantially perfluorinated and can be linear or branched, and which can contain H, Cl or Br atoms and can contain catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms of the skeletal chain, such hetero atoms providing stable linkages between fluorocarbon portions of the chain; fluorosulfonyl substituted perfluoroalkyl groups; fluorocarbonyl groups;
fluorocarbonyl substituted perfluoroalkyl groups;
alkoxycarbonyl substituted perfluoroalkyl groups; or the R1 and R2 together with the -?- group can form a 4- to 7-membered ring; each of R1 and R2 having no more than 20 carbon atoms.
7. The process of claim 1 wherein said fluorinated carbonyl compound is represented by the formula II
where X is H, F, Cl, Br, RO?- where R is lower alkyl, FSO2-, or F?-; and Rf' is a fluoroalkylene group, having 1 to 20 carbon atoms, which is substantially perfluorinated and can be linear or branched, and which can contain one or more H, Cl, or sr atoms, and can contain catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms of the skeletal chain, such hetero atoms providing stable linkages between fluorocarbon portions of the chain.
where X is H, F, Cl, Br, RO?- where R is lower alkyl, FSO2-, or F?-; and Rf' is a fluoroalkylene group, having 1 to 20 carbon atoms, which is substantially perfluorinated and can be linear or branched, and which can contain one or more H, Cl, or sr atoms, and can contain catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms of the skeletal chain, such hetero atoms providing stable linkages between fluorocarbon portions of the chain.
8. The process of claim 1 wherein said fluorinated carbonyl compound is COF2, FCOCOF, CF3COF, C2F5COF, n-C3F7COF, i-C3F7COF, C2F5OCF2COF, C3F7OC(CF3)FCOF, C3F7O[C(CF3)FCF2O]3C(CF3)FCOF, C2F5OCF2CF2OCF2COF, H(CF2)6COF, BrCF2COF, ClCF2COF, FSO2(CF2)3COF, CF3COCF3, HCF2COCF2H, FOCCF2CF2COF, FOCCF2CF2COOCH3, C7F15COF, CF3COCF2OC(CF3)FCOOCH3, CH3SO2CF2CF2COCF3, CF3CFHCOF, C3F7OC(CF2Cl)FCOF, C3F7OC(CF2Cl)FCF2OC(CF2Cl)FCOF, (C2F5)2NCF2COF, FOCC(CF3)FOCF2CF2COOCH3, FOCC(CF3)FOCF2CF2COOC2H5,
9. The process of claim 1 wherein said catalyst is potassium iodide or potassium bromide.
10. The process of claim 1 wherein said fluorinated carbonyl compound is tetrafluorosuccinyl fluoride, trifluoroacetal fluoride, carbonyl fluoride, hexafluoroacetone, heptafluorobutyryl fluoride, 4-(fluorosulfonyl)hexafluorobutyryl fluoride, or pentadecafluorooctanyl fluoride and said catalyst is potassium iodide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/906,816 US4749526A (en) | 1986-09-12 | 1986-09-12 | Process for preparing fluoraliphatic ether-containing carbonyl fluoride compositions |
| US906,816 | 1986-09-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1296355C true CA1296355C (en) | 1992-02-25 |
Family
ID=25423029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000545509A Expired - Fee Related CA1296355C (en) | 1986-09-12 | 1987-08-27 | Process for preparing fluoroaliphatic ether-containing carbonyl fluoride compositions |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4749526A (en) |
| EP (1) | EP0265052B1 (en) |
| JP (1) | JP2525426B2 (en) |
| KR (1) | KR950008283B1 (en) |
| AU (1) | AU601481B2 (en) |
| CA (1) | CA1296355C (en) |
| DE (1) | DE3761762D1 (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5153322A (en) * | 1987-10-30 | 1992-10-06 | Minnesota Mining And Manufacturing Company | Perfluoro (cycloaliphatic methyleneoxyalkylene) carbonyl fluorides and derivatives thereof |
| US4889656A (en) * | 1987-10-30 | 1989-12-26 | Minnesota Mining And Manufacturing Company | Perfluoro(cycloaliphatic methyleneoxyalkylene) carbonyl fluorides and derivatives thereof |
| US5210282A (en) * | 1987-10-30 | 1993-05-11 | Minnesota Mining And Manufacturing Company | Perfluoro(cycloaliphatic methyleneoxyalkylene) carbonyl fluorides and derivatives thereof |
| DE3737920A1 (en) * | 1987-11-07 | 1989-05-18 | Hoechst Ag | METHOD FOR PRODUCING PERFLUORED CARBONIC ACID FLUORIDES |
| EP0609200A1 (en) * | 1988-12-02 | 1994-08-10 | Minnesota Mining And Manufacturing Company | Direct fluorination process for making perfluorinated organic substances |
| IT1230163B (en) * | 1989-06-28 | 1991-10-14 | Ausimont Srl | PROCEDURE FOR THE PREPARATION OF BROMODIFLUOROACETILFLUORURO. |
| JP2523936B2 (en) * | 1990-05-18 | 1996-08-14 | 株式会社トクヤマ | Method for producing dicarbonyl fluoride |
| JP2855081B2 (en) * | 1994-10-31 | 1999-02-10 | 信越化学工業株式会社 | Method for producing amide compound |
| US5777179A (en) * | 1996-05-24 | 1998-07-07 | E. I. Du Pont De Nemours And Company | Co-production of perfluoromethyl perfluorovinyl ether and perfluoroethyl perfluorovinyl ether |
| US6015838A (en) * | 1996-11-04 | 2000-01-18 | 3M Innovative Properties Company | Aqueous film-forming foam compositions |
| US5998521A (en) * | 1996-11-04 | 1999-12-07 | 3M Innovative Properties Company | Aqueous fluoropolymer compositions and method of preparing the same |
| US6211415B1 (en) | 1996-11-22 | 2001-04-03 | Daikin Industries, Ltd. | Process for thermal decomposition of hexafluoropropylene oxide oligomers |
| JP3292072B2 (en) * | 1996-12-02 | 2002-06-17 | 信越化学工業株式会社 | Method for polymerizing hexafluoropropene oxide |
| ATE367371T1 (en) * | 1999-03-23 | 2007-08-15 | Asahi Glass Co Ltd | METHOD FOR PRODUCING FLUORINE COMPOUNDS USING LIQUID PHASE FLUORATION |
| KR100739239B1 (en) * | 1999-07-20 | 2007-07-18 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Use of Fluorinated Ketones in Fire Extinguishing Compositions |
| WO2001046093A2 (en) * | 1999-12-20 | 2001-06-28 | Asahi Glass Company, Limited | Process for producing a fluoride compound |
| ATE373633T1 (en) | 2000-07-11 | 2007-10-15 | Asahi Glass Co Ltd | METHOD FOR PRODUCING FLUORINE-CONTAINING COMPOUNDS |
| EP1346980B1 (en) | 2000-11-28 | 2011-05-18 | Asahi Glass Company Ltd. | Process for producing fluorosulfonyl fluoride compound |
| EP1352892B1 (en) | 2001-01-16 | 2010-06-09 | Asahi Glass Company Ltd. | Processes for producing fluorinated ester, fluorinated acyl fluoride, and fluorinated vinyl ether |
| US6624328B1 (en) * | 2002-12-17 | 2003-09-23 | 3M Innovative Properties Company | Preparation of perfluorinated vinyl ethers having a sulfonyl fluoride end-group |
| US20040116742A1 (en) * | 2002-12-17 | 2004-06-17 | 3M Innovative Properties Company | Selective reaction of hexafluoropropylene oxide with perfluoroacyl fluorides |
| US7348088B2 (en) * | 2002-12-19 | 2008-03-25 | 3M Innovative Properties Company | Polymer electrolyte membrane |
| JP4967297B2 (en) * | 2004-10-26 | 2012-07-04 | 旭硝子株式会社 | Novel ester and method for producing the same |
| US7211679B2 (en) * | 2005-03-09 | 2007-05-01 | 3M Innovative Properties Company | Perfluoroether acyl oligothiophene compounds |
| US7151276B2 (en) * | 2005-03-09 | 2006-12-19 | 3M Innovative Properties Company | Semiconductors containing perfluoroether acyl oligothiophene compounds |
| JP2007186454A (en) * | 2006-01-13 | 2007-07-26 | Yunimatekku Kk | Fluorine-containing ether alcohol and method for producing the same |
| JP5521463B2 (en) * | 2008-10-01 | 2014-06-11 | ダイキン工業株式会社 | Fluoroethercarboxylic acid fluoride and method for producing fluoroethercarboxylic acid |
| JP5267632B2 (en) * | 2011-10-06 | 2013-08-21 | ダイキン工業株式会社 | Method for producing fluorinated (poly) ether-containing carbonyl fluoride |
| JP6256948B2 (en) * | 2014-02-28 | 2018-01-10 | 三菱マテリアル電子化成株式会社 | Nonionic fluorine-containing surfactant, method for producing the same, and fluorine resin dispersant |
| KR102425264B1 (en) * | 2020-07-07 | 2022-07-26 | 한국화학연구원 | Method for preparing hexafluoropropylene oxide dimer with high conversion rate |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3114778A (en) * | 1963-12-17 | Fluorinated vinyl ethers and their | ||
| US2910490A (en) * | 1956-10-16 | 1959-10-27 | Jefferson Chem Co Inc | Process for preparing glycol monoesters of organic carboxylic acids |
| DE1257772B (en) * | 1961-12-08 | |||
| US3250806A (en) * | 1962-04-05 | 1966-05-10 | Du Pont | Fluorocarbon ethers of tetrafluoroethylene epoxide |
| US3250808A (en) * | 1963-10-31 | 1966-05-10 | Du Pont | Fluorocarbon ethers derived from hexafluoropropylene epoxide |
| US3409647A (en) * | 1965-06-24 | 1968-11-05 | Agriculture Usa | Certain fluorinated carboxylic acids and their derivatives |
| US3311658A (en) * | 1966-08-01 | 1967-03-28 | Du Pont | Fluorocarbon ethers containing iodine |
| US3699156A (en) * | 1967-01-11 | 1972-10-17 | Air Prod & Chem | Fluorinated cyclic alcohol and their esters |
| DE2461445C2 (en) * | 1974-12-24 | 1984-06-28 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of perfluoro-α-alkoxypropionic acid fluorides |
| JPS5935379B2 (en) * | 1975-04-02 | 1984-08-28 | イ−・アイ・デュポン・デ・ニモアス・アンド・カンパニ− | Contact reaction method of hexafluoropropylene epoxide and ketone or acid fluoride |
| DE2627986C2 (en) * | 1976-06-23 | 1985-02-14 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of perfluoroalkoxypropionic acid fluorides |
-
1986
- 1986-09-12 US US06/906,816 patent/US4749526A/en not_active Expired - Lifetime
-
1987
- 1987-08-25 EP EP87307480A patent/EP0265052B1/en not_active Expired - Lifetime
- 1987-08-25 DE DE8787307480T patent/DE3761762D1/en not_active Expired - Fee Related
- 1987-08-27 CA CA000545509A patent/CA1296355C/en not_active Expired - Fee Related
- 1987-09-08 AU AU78144/87A patent/AU601481B2/en not_active Ceased
- 1987-09-10 JP JP62227540A patent/JP2525426B2/en not_active Expired - Lifetime
- 1987-09-10 KR KR1019870010013A patent/KR950008283B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2525426B2 (en) | 1996-08-21 |
| US4749526A (en) | 1988-06-07 |
| DE3761762D1 (en) | 1990-04-05 |
| AU601481B2 (en) | 1990-09-13 |
| EP0265052A1 (en) | 1988-04-27 |
| EP0265052B1 (en) | 1990-02-28 |
| KR880003888A (en) | 1988-06-01 |
| KR950008283B1 (en) | 1995-07-27 |
| AU7814487A (en) | 1988-03-17 |
| JPS6377835A (en) | 1988-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1296355C (en) | Process for preparing fluoroaliphatic ether-containing carbonyl fluoride compositions | |
| EP0706506B1 (en) | Fluorinated bis-ethers and process for preparing them and fluorinated methyl ethers | |
| JP3572077B2 (en) | Method for producing perfluoroalkyl iodides | |
| US20040116742A1 (en) | Selective reaction of hexafluoropropylene oxide with perfluoroacyl fluorides | |
| US6054626A (en) | Synthesis of fluorinated ethers | |
| CA1339538C (en) | Process for the preparation of fluorohalogenated ethers starting from fluorooxy-compounds and halogenated olefins | |
| CA1082719A (en) | Fluorine containing ketones | |
| EP0048544B1 (en) | Preparation of difluoromalonyl fluoride | |
| US2980740A (en) | alpha, alpha, omega-trihydroperfluoroalkanes | |
| US3449389A (en) | Primary fluorocarbon alkoxides | |
| US5457238A (en) | Process for the preparation of fluoroketones | |
| KR101125167B1 (en) | Process for preparing fluorohalogenethers | |
| US4334099A (en) | Preparation of hexafluoroacetone from hexafluorothioacetone dimer | |
| CA1164016A (en) | Liquid phase synthesis of hexafluoroisobutylene | |
| CA1339037C (en) | Branched perfluoroalkyl halides and preparation thereof | |
| WO1995023795A2 (en) | Process for preparing polyfluorooxetanes | |
| Dear et al. | Polyalo ethers from the reaction of fluoro alcohols and halo olefins | |
| EP0504285B1 (en) | Fluorocarbon compounds and processes for preparation thereof | |
| US3996200A (en) | Perfluorinated para-diketone polymers | |
| JP3128967B2 (en) | Method for producing 1-bromo-2-iodotetrafluoroethane | |
| CA1318327C (en) | 2,2-difluoropropionic acid derivatives | |
| US3621066A (en) | Substituted halocycloalkenes | |
| EP0764624B1 (en) | Process for the preparation of fluoroketones | |
| JPH0830021B2 (en) | Method for producing fluorine-containing ether compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |