CA2190054A1 - Process for the preparation of perfluoropropionyl fluoride - Google Patents
Process for the preparation of perfluoropropionyl fluorideInfo
- Publication number
- CA2190054A1 CA2190054A1 CA002190054A CA2190054A CA2190054A1 CA 2190054 A1 CA2190054 A1 CA 2190054A1 CA 002190054 A CA002190054 A CA 002190054A CA 2190054 A CA2190054 A CA 2190054A CA 2190054 A1 CA2190054 A1 CA 2190054A1
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- Prior art keywords
- radicals
- iii
- carbon atoms
- formula
- atom
- 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.)
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Classifications
-
- 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
The invention relates to a process for the preparation of perfluoropropionyl fluoride (??) by the isomerization of hexafluoropropene oxide (?):
? I II
wherein the reaction medium used is a liquid complex ammonium hydrofluoride.
? I II
wherein the reaction medium used is a liquid complex ammonium hydrofluoride.
Description
21~00S~
HOECHST AKTIENGESELLSCHAFT HOE 95/F 261 Dr. KM/gp Description 5 Process for the ~ pdl dLiun of perfl~ol u~, upio, Iyl fluoride The present invention relates to a process for the selective ~ pa, dlion of perfl~o, u,u, u~,iu"yl fluoride (ll) by the iso~ dLiù,~ of hexafl~ u,u~ ul ~"e oxide (I):
/O\ ~O
CF3 --CF--CF2 ' CF3 -- CF2--C
II
Hexafluo, u~, up~"e oxide (I) and perfluu, u~ l U,UiCJI Iyl fluoride (Il) are the starting materials for the p, I::,Udl d~iOIl of perfluoro(n-propyl vinyl ether),PPVE, a valuable cu" ,u,~o, "~r for the production of modified polytetrafluoroethylene. PPVE is prepared according to the following 20 scheme:
~ /o\
CF3 CF2 C~ + fF CF
II
O
3û III CF3 CF3 CF2 CF --O --CF = CF2 + COF2 P PVE
, . 21gO05~
HOECHST AKTIENGESELLSCHAFT HOE 95/F 261 Dr. KM/gp Description 5 Process for the ~ pdl dLiun of perfl~ol u~, upio, Iyl fluoride The present invention relates to a process for the selective ~ pa, dlion of perfl~o, u,u, u~,iu"yl fluoride (ll) by the iso~ dLiù,~ of hexafl~ u,u~ ul ~"e oxide (I):
/O\ ~O
CF3 --CF--CF2 ' CF3 -- CF2--C
II
Hexafluo, u~, up~"e oxide (I) and perfluu, u~ l U,UiCJI Iyl fluoride (Il) are the starting materials for the p, I::,Udl d~iOIl of perfluoro(n-propyl vinyl ether),PPVE, a valuable cu" ,u,~o, "~r for the production of modified polytetrafluoroethylene. PPVE is prepared according to the following 20 scheme:
~ /o\
CF3 CF2 C~ + fF CF
II
O
3û III CF3 CF3 CF2 CF --O --CF = CF2 + COF2 P PVE
, . 21gO05~
Hexafl~olu~,uu~lle oxide (I) can thus be attacked by its own isu",~ dliu"
product (Il) to form an ether-carboxylic acid fluoride (Ill). Analogously to the reaction of (Il) with (I), however, it is also possible for (Ill) to react further with (I) to give a higher ether-carboxylic acid fluoride, which in tum 5 reacts with (I), ultimately forming perfluorinated polyether-carboxylic acid fluorides. The known p~ucesses for the i~u",el i~dLiol1 of hexafluu,u~,ul,el~e oxide (I) to perfluu~uplu~iul~yl fluoride (Il) therefore have cu"si.iel dule disadvantages as regards the selectivity or the reaction times.
1û
Thus for example, US-A-3 321 515 describes the iso" l~ dLiUI I of perfluorinated epoxides, which produces perfluorinated ketones in the presence of catalytic amounts of Lewis acids, but produces the cul, t:suo,~di"g acid fluorides in the presence of catalytic amounts of Lewis 15 bases. The Lewis acids used are acidic metal oxides and metal halides;
on the other hand, the Lewis bases used are fluorine ions in the form of alkali metal fluorides or compounds capable of producing fluorine ions in the reaction medium, e.g. tertiary amines (including pyridine), N-oxides thereof and tertiary acid amides. A number of examples in the said patent 2û describe the isu~e~i~d~iv~) of hexafluo,u,u,u~,e,le oxide (I) (HFPO) with basic catalysts to give perfluu, u,u, u,uiul Iyl fluoride (Il). This always involves the;,, ' " 1 of high pressures or very long reaction times, or both. In prindple, therefore, the reactions must be carried out in pressure vessels and the formation of an oily by-product is often " ,~"~k.ned. Directly added 25 fluoride is clearly rather unsuitable as the catalyst (Table ll, Ex. Method 9and 25), while amines (producing fluoride ions) give SUI I I~.~ ldl better results in some cases (Ex. Method 16, 20, 21, 33, 36, 38, 56). However, none of the catalysts described in US-A-3 321 515 effects a rapid and simultaneously pressureless iso",eri~dLiù,l of hexafluu~o,c,upe,,e oxide (I) 30 to perfluolu,u, UpiOI Iyl fluoride (Il) with high yields, as would be desirable for these two low-boiling substances.
Again, according to Japanese patent 04 134 046, published much later in1 99û, which likewise describes the iso",e, i~d~iUI I of hexafluol u,u, up~, ,e - ' 21~005~
product (Il) to form an ether-carboxylic acid fluoride (Ill). Analogously to the reaction of (Il) with (I), however, it is also possible for (Ill) to react further with (I) to give a higher ether-carboxylic acid fluoride, which in tum 5 reacts with (I), ultimately forming perfluorinated polyether-carboxylic acid fluorides. The known p~ucesses for the i~u",el i~dLiol1 of hexafluu,u~,ul,el~e oxide (I) to perfluu~uplu~iul~yl fluoride (Il) therefore have cu"si.iel dule disadvantages as regards the selectivity or the reaction times.
1û
Thus for example, US-A-3 321 515 describes the iso" l~ dLiUI I of perfluorinated epoxides, which produces perfluorinated ketones in the presence of catalytic amounts of Lewis acids, but produces the cul, t:suo,~di"g acid fluorides in the presence of catalytic amounts of Lewis 15 bases. The Lewis acids used are acidic metal oxides and metal halides;
on the other hand, the Lewis bases used are fluorine ions in the form of alkali metal fluorides or compounds capable of producing fluorine ions in the reaction medium, e.g. tertiary amines (including pyridine), N-oxides thereof and tertiary acid amides. A number of examples in the said patent 2û describe the isu~e~i~d~iv~) of hexafluo,u,u,u~,e,le oxide (I) (HFPO) with basic catalysts to give perfluu, u,u, u,uiul Iyl fluoride (Il). This always involves the;,, ' " 1 of high pressures or very long reaction times, or both. In prindple, therefore, the reactions must be carried out in pressure vessels and the formation of an oily by-product is often " ,~"~k.ned. Directly added 25 fluoride is clearly rather unsuitable as the catalyst (Table ll, Ex. Method 9and 25), while amines (producing fluoride ions) give SUI I I~.~ ldl better results in some cases (Ex. Method 16, 20, 21, 33, 36, 38, 56). However, none of the catalysts described in US-A-3 321 515 effects a rapid and simultaneously pressureless iso",eri~dLiù,l of hexafluu~o,c,upe,,e oxide (I) 30 to perfluolu,u, UpiOI Iyl fluoride (Il) with high yields, as would be desirable for these two low-boiling substances.
Again, according to Japanese patent 04 134 046, published much later in1 99û, which likewise describes the iso",e, i~d~iUI I of hexafluol u,u, up~, ,e - ' 21~005~
oxide (I) to perfluo, uu, u~io, Iyl fluoride (Il) in the presence of tertiary amines pyridines and quinolines the carboxylic acid fluoride is obtained after a reaction time of 4 h with a yield of only 61.9% of theory It is therefore obviously very difficult to prevent the perfl~ù~ up, uui~, Iyl fluoride 5 (Il) formed by iso,~ dlio,~ from reacting furtherwith hexafluu,uu,uue~le oxide (I). This further reaction has even been utilized s,pe,_iri~3 'y for the p, t:Udl dliUI, of mixtures of perfluorinated polyether-carboxylic acid fluorides. Thus according to DE-A-3 901 ûOO a mixture ûf oliuu~ ric ether-carboxylic acid fluorides of the general formula C2F5- [CF20CF (CF3) ] n-COF .
is obtained from hexafluo, uplupelle oxide (I) in an aprotic solvent in the presence of tetramethylethyl~"edid" ,i"e.
Against the background of this state of the art it was very surprising to f nd that hexafluu~uu~uuel1e oxide (I) is selectively iso",e,i~d to perfluo,uplupio,,yl fluoride (Il) under very mild conditions when a liquid complex ammonium hydrofluoride of the general formula (Ill):
20 [R R R NH] [H(n l)Fn] III
is used as the reaction medium. The isul"t~ d~iun proceeds so rapidly that the reaction can be carried out under pressureless conditions and it 25 becomes ~",1ecessd,y to use pressure-resistant reactors although the use of pressure has no adverse effects.
~ The present invention therefore provides a process for the p, ~pdl dLiul, of perfluu, up,uuiu, ,yl fluoride (Il) by the i~u, "t~ dliOI1 of hexafluu, up, uu~,~e 30 oxide (I):
/ o\ //o CF3 --CF--CF2 ~ ,CF3 -- CF2 --C
II
21900~
wherein the reaction medium used is a liquid complex ammonium hydrofluoride of the general formula (Ill):
[RlR2R3NH~ + [H F ] - III
in which n is an integer or fraction s3 and the radicals R1, R2 and R3 are identica! or different and each of these radicals is an alkyl radical having 1 to 20 carbon atoms, preferably 1 to 12 and especially 1 to 6 carbon atoms, a cycloalkyl radical having 5 to 7 carbon atoms, an aralkyl radical having 7 to 10 carbon atoms or an aryl radical having 6 to 10 carbon atoms which can also be sl IhCtitl It~d 15 by C1- to C3-alkyl or C1 to C3-alkoxy groups, or in which two of the radicals R1 to R3, together with the N atom which carries them, fomm a 5- to 7-" ,e" ,L,e, ~d ring which can contain an O atom or another N atom, or in which the radicals R1 to R3, together with the N atom which carries 20 them, form two or three 5- to 7-" ,t:" ,L,e, t:d saturated rings which can contain further N atoms, e.g. in ~, uLu, IdLt:d diazabicyclooctane, or in which the radicals R1 to R3 together form a 6-lll~lllb~l~d heterocyclic ring which can contain one or two N atoms and can also be benzo-fused, e.g. pyridinium, pyrimidinium or quinolinium.
If two of the radicals R1 to R3, together with the N atom which carries them, form a 5- to 7-1llt~ LJt~ d ring, this ring preferably does not contain an O
atom or another N atom.
30 Preferably, at least one of the radicals R1 to R3 is an alkyl radical having 1 to 12 carbon atoms, especially 1 to 6 carbon atoms.
Particularly preferably, all three radicals R1 to R3 are alkyl radicals and have a total of 3 to 12 carbon atoms; very particularly preferably, 2190U5~
R1 =R2=R3=CH3.
The number n in the general formula (Ill) is an integer or fraction s3,preferably 1 1 to 2.9 and especially 2 to 2.9.
The complex ammonium hydrofluorides can be prepared by reacting the amines directly with HF in the desired molar ratio. The nitrogen atom of the amine is plulvlld~d in this reaction; additional HF molecules combine with the fluorine ion to form complex hydrofluoride anions. Some 10 examples of the complex tertiary ammonium hydrofluorides of the general fonmula (Ill) which can be used in the process accordin~ to the invention are given below:
(cH3)3NH Hl.8F2.8 ( C2H5 ) 3NH Hl, 8 F2 . 8 (n - C3 H7 ) 3NH H2 F3 (i-C3H7) 2 (C2H5 ) NH Hl, 6F2 . 6 (n-C4Hg) 3NH Hl 6F2 .6 [ (CH3 ) 2NH-CH2 ~] 2 [Hl 35F2 .35] 2 CN--CH3 Hl . 8F2 . 8 ~N--H Hl 7F2 7 H
N ( CH3 ) 2 Hl, 6 F 2 . 6 - 21 g~OS~
Complex hydrofluorides of this type are known in literature, e.g. from Bull.
Soc. Chim. France 1965, pages 1890 to 1892, or from J. Fluorine Chemistry 15 (1980), pages 423 to 434. These are stable Cul I l,ulex~s with no hydrogen fluoride vapor pressure at all, so they are easy to handle and 5 in some cases can even be distilled in borosilicate glass apparatuses.
The i:~U~ dliUI I process according to the invention can be carried outunder anhydrous conditions in pressure reactors, e.g. stirred autoclaves, in the manner conventionally used for gaseous/liquid reaction mixtures.
1û However, a pressureless procedure in a bubble column is preferred. The use of bubble columns for suitable gas-liquid reactions is state of the art;
the dUpl Upl idle requirements are known to those skilled in the art.
The temperature is not critical in terms of the isu",e, i~d~iOr~ process itself,15 but rather depends on the properties of the complex tertiary ammonium hydrofluoride (Ill) used as the reaction medium, i.e. on its freezing point, itstemperature-depend~"l viscosity when using a bubble column, and its de~u" ~,uo~i~io,~ point. The isu" ,e, i d~iOIl temperature is generally 0 to 100~C but preferably 40 to 80~C.
Example 1:
600 9 of the liquid complex ammonium hydrofluoride [ (CX3) 3N~] [Hl 8F2 . 8]
were introduced as the medium, up to a height of 160 cm, into an externally heated glass tube of length 2 m and internal diameter 25 mm, which was equipped as a bubble column and lined with a ~Idll::lUdlt~
30 tetrafluoroethylene/hexafluo,u,o~ou~,~e copolymer (FEP), and were heated to 60C C. Hexafl~u, u,u, u,uene oxide was then introduced at the foot of the bubble column and finely dispersed in the medium. The product gas emerging at the head of the bubble column was condensed in a trap cooled with dry i~ l Idl 1~1. The cu, Idt:l ISd~ 3 was examined by 19F NMR
, ~ 21900S~
:~ue~ L~ us. ~uy. A conversion of 95 mol% was del~", lil ,ed on the basis of the amount of hexafluu, uul up~ e oxide used; the yield of perfl~ul uu, uuiul Iyl fluoride was 97.9 mol% on the basis of this conversion.
5 Example 2:
The reaction described in Example 1 was repeated except that the temperature was only 30~C. Because the viscosity of the medium was now higher the throughput applied to the bubble column was lower than in Example 1; the residence time of the gas in thè medium was 10 u ul I ~ JUI l.lil Iyly longer. According to NMR analysis of the product gas the conversion was 95.g mol% on the basis of the amount of hexafl~u, UfJI u~uelle oxide used; on the other hand the yield of perfiuu, uul uuiol Iyl fluoride on the basis of this conversion was practically 10û mol%.
Example 3:
The reaction described in Example 1 was repeated except that the bubble column was kept at a temperature of 80~C. According to NMR analysis of the product gas the conversion was 88 mol% on the basis of the amount 2û of hexafluu, u,o, up~ne oxide used; the yield of perfluu, uu, UIJiUI Iyl fluoride on the basis of this conversion was 98 mol%.
Example 4:
52û 9 of the liquid complex ammonium hydrofluoride [ ( n - c4H9 ) 3 NH] [Hl . lF2 .1]
were introduced to a height of 150 cm into the bubble column described in 30 Example 1 and were heated to 60~C. The introduction of hexaflu~, uu, upe,~e oxide and the analysis were then performed as described in Example 1. The conversion of the hexafl~u, uu, u,uene oxide used was 1ûû mol%; the product gas contained 96 mol% of perfluu, uul u,uio, Iyl fluoride.
~ ~19005~
Example 5:
The reaction described in Example 4 was carried out at a temperature of 70~C. According to NMR analysis the conversion of the hexafluo, uu, upe~le oxide used was again 100 mol%; the product gas 5 contained 99 mol% of perfluul uu, upi~l Iyl fluoride.
Example 6:
100 3 of the liquid complex ammonium hydrofluoride 0 [ (n-c4H9) 3~H] [Hl .lF2 .1]
were placed in a stirred autoclave of 300 ml capacity (material: ~Hastelloy C) and about 20 9 of hexafluu, uu, upel~e oxide were introduced under pressure from a pressurized storage bottle. The reaction mixture was 51 Ihseq~l~ntly heated at 60~C for 2 h under autogenous pressure with stirring and the pressure was then released via a cooling trap in a dry ice bath. According to 19F NMR analysis the gas mixture contained perfluu,uu,u~i~"yl fluoride in a collcell~ldLio,~ of 97.3 mol% togetherwith 2.6 mol% of unreacted hexafluoluu,upt:"e oxide. No dilll~ dliol~ or ~ligo,,,~ dLio,l products of hexafluo,u,u,u~ e were d~ le either in the contents of the cold trap or in the hydrofluoride residue remaining in the autoclave.
is obtained from hexafluo, uplupelle oxide (I) in an aprotic solvent in the presence of tetramethylethyl~"edid" ,i"e.
Against the background of this state of the art it was very surprising to f nd that hexafluu~uu~uuel1e oxide (I) is selectively iso",e,i~d to perfluo,uplupio,,yl fluoride (Il) under very mild conditions when a liquid complex ammonium hydrofluoride of the general formula (Ill):
20 [R R R NH] [H(n l)Fn] III
is used as the reaction medium. The isul"t~ d~iun proceeds so rapidly that the reaction can be carried out under pressureless conditions and it 25 becomes ~",1ecessd,y to use pressure-resistant reactors although the use of pressure has no adverse effects.
~ The present invention therefore provides a process for the p, ~pdl dLiul, of perfluu, up,uuiu, ,yl fluoride (Il) by the i~u, "t~ dliOI1 of hexafluu, up, uu~,~e 30 oxide (I):
/ o\ //o CF3 --CF--CF2 ~ ,CF3 -- CF2 --C
II
21900~
wherein the reaction medium used is a liquid complex ammonium hydrofluoride of the general formula (Ill):
[RlR2R3NH~ + [H F ] - III
in which n is an integer or fraction s3 and the radicals R1, R2 and R3 are identica! or different and each of these radicals is an alkyl radical having 1 to 20 carbon atoms, preferably 1 to 12 and especially 1 to 6 carbon atoms, a cycloalkyl radical having 5 to 7 carbon atoms, an aralkyl radical having 7 to 10 carbon atoms or an aryl radical having 6 to 10 carbon atoms which can also be sl IhCtitl It~d 15 by C1- to C3-alkyl or C1 to C3-alkoxy groups, or in which two of the radicals R1 to R3, together with the N atom which carries them, fomm a 5- to 7-" ,e" ,L,e, ~d ring which can contain an O atom or another N atom, or in which the radicals R1 to R3, together with the N atom which carries 20 them, form two or three 5- to 7-" ,t:" ,L,e, t:d saturated rings which can contain further N atoms, e.g. in ~, uLu, IdLt:d diazabicyclooctane, or in which the radicals R1 to R3 together form a 6-lll~lllb~l~d heterocyclic ring which can contain one or two N atoms and can also be benzo-fused, e.g. pyridinium, pyrimidinium or quinolinium.
If two of the radicals R1 to R3, together with the N atom which carries them, form a 5- to 7-1llt~ LJt~ d ring, this ring preferably does not contain an O
atom or another N atom.
30 Preferably, at least one of the radicals R1 to R3 is an alkyl radical having 1 to 12 carbon atoms, especially 1 to 6 carbon atoms.
Particularly preferably, all three radicals R1 to R3 are alkyl radicals and have a total of 3 to 12 carbon atoms; very particularly preferably, 2190U5~
R1 =R2=R3=CH3.
The number n in the general formula (Ill) is an integer or fraction s3,preferably 1 1 to 2.9 and especially 2 to 2.9.
The complex ammonium hydrofluorides can be prepared by reacting the amines directly with HF in the desired molar ratio. The nitrogen atom of the amine is plulvlld~d in this reaction; additional HF molecules combine with the fluorine ion to form complex hydrofluoride anions. Some 10 examples of the complex tertiary ammonium hydrofluorides of the general fonmula (Ill) which can be used in the process accordin~ to the invention are given below:
(cH3)3NH Hl.8F2.8 ( C2H5 ) 3NH Hl, 8 F2 . 8 (n - C3 H7 ) 3NH H2 F3 (i-C3H7) 2 (C2H5 ) NH Hl, 6F2 . 6 (n-C4Hg) 3NH Hl 6F2 .6 [ (CH3 ) 2NH-CH2 ~] 2 [Hl 35F2 .35] 2 CN--CH3 Hl . 8F2 . 8 ~N--H Hl 7F2 7 H
N ( CH3 ) 2 Hl, 6 F 2 . 6 - 21 g~OS~
Complex hydrofluorides of this type are known in literature, e.g. from Bull.
Soc. Chim. France 1965, pages 1890 to 1892, or from J. Fluorine Chemistry 15 (1980), pages 423 to 434. These are stable Cul I l,ulex~s with no hydrogen fluoride vapor pressure at all, so they are easy to handle and 5 in some cases can even be distilled in borosilicate glass apparatuses.
The i:~U~ dliUI I process according to the invention can be carried outunder anhydrous conditions in pressure reactors, e.g. stirred autoclaves, in the manner conventionally used for gaseous/liquid reaction mixtures.
1û However, a pressureless procedure in a bubble column is preferred. The use of bubble columns for suitable gas-liquid reactions is state of the art;
the dUpl Upl idle requirements are known to those skilled in the art.
The temperature is not critical in terms of the isu",e, i~d~iOr~ process itself,15 but rather depends on the properties of the complex tertiary ammonium hydrofluoride (Ill) used as the reaction medium, i.e. on its freezing point, itstemperature-depend~"l viscosity when using a bubble column, and its de~u" ~,uo~i~io,~ point. The isu" ,e, i d~iOIl temperature is generally 0 to 100~C but preferably 40 to 80~C.
Example 1:
600 9 of the liquid complex ammonium hydrofluoride [ (CX3) 3N~] [Hl 8F2 . 8]
were introduced as the medium, up to a height of 160 cm, into an externally heated glass tube of length 2 m and internal diameter 25 mm, which was equipped as a bubble column and lined with a ~Idll::lUdlt~
30 tetrafluoroethylene/hexafluo,u,o~ou~,~e copolymer (FEP), and were heated to 60C C. Hexafl~u, u,u, u,uene oxide was then introduced at the foot of the bubble column and finely dispersed in the medium. The product gas emerging at the head of the bubble column was condensed in a trap cooled with dry i~ l Idl 1~1. The cu, Idt:l ISd~ 3 was examined by 19F NMR
, ~ 21900S~
:~ue~ L~ us. ~uy. A conversion of 95 mol% was del~", lil ,ed on the basis of the amount of hexafluu, uul up~ e oxide used; the yield of perfl~ul uu, uuiul Iyl fluoride was 97.9 mol% on the basis of this conversion.
5 Example 2:
The reaction described in Example 1 was repeated except that the temperature was only 30~C. Because the viscosity of the medium was now higher the throughput applied to the bubble column was lower than in Example 1; the residence time of the gas in thè medium was 10 u ul I ~ JUI l.lil Iyly longer. According to NMR analysis of the product gas the conversion was 95.g mol% on the basis of the amount of hexafl~u, UfJI u~uelle oxide used; on the other hand the yield of perfiuu, uul uuiol Iyl fluoride on the basis of this conversion was practically 10û mol%.
Example 3:
The reaction described in Example 1 was repeated except that the bubble column was kept at a temperature of 80~C. According to NMR analysis of the product gas the conversion was 88 mol% on the basis of the amount 2û of hexafluu, u,o, up~ne oxide used; the yield of perfluu, uu, UIJiUI Iyl fluoride on the basis of this conversion was 98 mol%.
Example 4:
52û 9 of the liquid complex ammonium hydrofluoride [ ( n - c4H9 ) 3 NH] [Hl . lF2 .1]
were introduced to a height of 150 cm into the bubble column described in 30 Example 1 and were heated to 60~C. The introduction of hexaflu~, uu, upe,~e oxide and the analysis were then performed as described in Example 1. The conversion of the hexafl~u, uu, u,uene oxide used was 1ûû mol%; the product gas contained 96 mol% of perfluu, uul u,uio, Iyl fluoride.
~ ~19005~
Example 5:
The reaction described in Example 4 was carried out at a temperature of 70~C. According to NMR analysis the conversion of the hexafluo, uu, upe~le oxide used was again 100 mol%; the product gas 5 contained 99 mol% of perfluul uu, upi~l Iyl fluoride.
Example 6:
100 3 of the liquid complex ammonium hydrofluoride 0 [ (n-c4H9) 3~H] [Hl .lF2 .1]
were placed in a stirred autoclave of 300 ml capacity (material: ~Hastelloy C) and about 20 9 of hexafluu, uu, upel~e oxide were introduced under pressure from a pressurized storage bottle. The reaction mixture was 51 Ihseq~l~ntly heated at 60~C for 2 h under autogenous pressure with stirring and the pressure was then released via a cooling trap in a dry ice bath. According to 19F NMR analysis the gas mixture contained perfluu,uu,u~i~"yl fluoride in a collcell~ldLio,~ of 97.3 mol% togetherwith 2.6 mol% of unreacted hexafluoluu,upt:"e oxide. No dilll~ dliol~ or ~ligo,,,~ dLio,l products of hexafluo,u,u,u~ e were d~ le either in the contents of the cold trap or in the hydrofluoride residue remaining in the autoclave.
Claims (7)
1. A process for the preparation of perfluoropropionyl fluorides (II) by the isomerization of hexafluoropropene oxide (I):
? I II
wherein the reaction medium used is a liquid complex ammonium hydrofluoride of the general formula (III):
[R1R2R3NH] + [H(n-1)Fn]Fn]- III
in which n is an integer or fraction ~ 3 and the radicals R1, R2 and R3 are identical or different and each of these radicals is an alkyl radical having 1 to 20 carbon atoms, a cycloalkyl radical having 5 to 7 carbon atoms, an aralkyl radical having 7 to 10 carbon atoms or an aryl radical having 6 to 10 carbon atoms which can also be substituted by C1- to C3-alkyl or C1 to C3-alkoxy groups, or in which two of the radicals R1 to R3, together with the N atom which carries them, form a 5- to 7-membered ring which can contain an O atom or another N atom, or in which the radicals R1 to R3, together with the N atom which carries them, form two or three 5- to 7-membered saturated rings which can contain further N atoms, or in which the radicals R1 to R3 together form a 6-membered heterocyclic ring which can contain one or two N atoms and can also be benzo-fused.
? I II
wherein the reaction medium used is a liquid complex ammonium hydrofluoride of the general formula (III):
[R1R2R3NH] + [H(n-1)Fn]Fn]- III
in which n is an integer or fraction ~ 3 and the radicals R1, R2 and R3 are identical or different and each of these radicals is an alkyl radical having 1 to 20 carbon atoms, a cycloalkyl radical having 5 to 7 carbon atoms, an aralkyl radical having 7 to 10 carbon atoms or an aryl radical having 6 to 10 carbon atoms which can also be substituted by C1- to C3-alkyl or C1 to C3-alkoxy groups, or in which two of the radicals R1 to R3, together with the N atom which carries them, form a 5- to 7-membered ring which can contain an O atom or another N atom, or in which the radicals R1 to R3, together with the N atom which carries them, form two or three 5- to 7-membered saturated rings which can contain further N atoms, or in which the radicals R1 to R3 together form a 6-membered heterocyclic ring which can contain one or two N atoms and can also be benzo-fused.
2. The process as claimed in claim 1, wherein an ammonium hydrofluoride of the formula (III) is used in which at least one of the radicals R1 to R3 is an alkyl radical having 1 to 12 carbon atoms.
3. The process as claimed in claim 1, wherein an ammonium hydrofluoride of the formula (III) is used in which at least one of the radicals R1 to R3 is an alkyl radical having 1 to 6 carbon atoms.
4. The process as claimed in claim 1, wnereln an ammonium hydrofluoride of the formula (III) is used in which all three radicals R1 to R3 are alkyl radicals and have a total of 3 to 12 carbon atoms.
5. The process as claimed in claim 1, wherein an ammonium hydrofluoride of the fonmula (III) is used in which R1 = R2 = R3 = CH3.
6. The process as claimed in one of claims 1 to 5, wherein an ammonium hydrofluoride of the formula (III) is used in which n is an integer or fraction from 1.1 to 2.9.
7. The process as claimed in one of claims 1 to 5, wherein an ammonium hydrofluoride of the formula (III) is used in which n is an integer or fraction from 2 to 2.9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19542190A DE19542190A1 (en) | 1995-11-13 | 1995-11-13 | Process for the preparation of perfluoropropionyl fluoride |
| DE19542190.6 | 1995-11-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2190054A1 true CA2190054A1 (en) | 1997-05-14 |
Family
ID=7777290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002190054A Abandoned CA2190054A1 (en) | 1995-11-13 | 1996-11-12 | Process for the preparation of perfluoropropionyl fluoride |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5684193A (en) |
| EP (1) | EP0773208A1 (en) |
| JP (1) | JPH09183747A (en) |
| CA (1) | CA2190054A1 (en) |
| DE (1) | DE19542190A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100113691A1 (en) * | 2008-11-06 | 2010-05-06 | E. I. Du Pont De Nemours And Company | Fluoro olefin polymerization |
| CN103145544A (en) * | 2011-12-06 | 2013-06-12 | 中化蓝天集团有限公司 | Method for synthesis of pentafluoropropionyl fluoride |
| CN105315150A (en) * | 2014-08-04 | 2016-02-10 | 天津市长芦盐业总公司化工新材料工程技术中心 | Method for preparing perfluoropropionyl fluoride from hexafluoropropylene oxide oligomer |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3321515A (en) | 1963-04-24 | 1967-05-23 | Du Pont | Method of making fluorinated carbonyl compounds |
| DE1468775A1 (en) * | 1964-10-23 | 1969-03-06 | Du Pont | Process for the preparation of fluorinated saturated aliphatic carboxylic acid fluorides |
| GB1295174A (en) * | 1970-02-16 | 1972-11-01 | ||
| DE3737920A1 (en) * | 1987-11-07 | 1989-05-18 | Hoechst Ag | METHOD FOR PRODUCING PERFLUORED CARBONIC ACID FLUORIDES |
| DE3901000A1 (en) | 1989-01-14 | 1990-07-19 | Hoechst Ag | METHOD FOR OLIGOMERIZING HEXAFLUORPROPENOXIDE |
| DE3901002A1 (en) * | 1989-01-14 | 1990-07-26 | Hoechst Ag | METHOD FOR DIMERIZING HEXAFLUOROPROPENOXIDE |
| JPH04134064A (en) * | 1990-09-25 | 1992-05-07 | Otsuu Kenkyusho | Production of 4-alkoxyindole derivative |
-
1995
- 1995-11-13 DE DE19542190A patent/DE19542190A1/en not_active Withdrawn
-
1996
- 1996-11-07 EP EP96117830A patent/EP0773208A1/en not_active Withdrawn
- 1996-11-11 JP JP8298709A patent/JPH09183747A/en not_active Withdrawn
- 1996-11-12 CA CA002190054A patent/CA2190054A1/en not_active Abandoned
- 1996-11-12 US US08/745,816 patent/US5684193A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09183747A (en) | 1997-07-15 |
| US5684193A (en) | 1997-11-04 |
| DE19542190A1 (en) | 1997-05-15 |
| EP0773208A1 (en) | 1997-05-14 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Discontinued |
Effective date: 19991112 |