FR2528855A1 - USE OF PERFLUOROALLYL FLUOROSULFATE - Google Patents

Abstract

THE INVENTION RELATES TO FLUORINE ORGANIC COMPOUNDS. IT CONCERNS THE USE OF PERFLUOROALLYL FLUOROSULFATE FOR THE PREPARATION OF HOMOPOLYMERS AND COPOLYMERS WITH FLUOROETHYLENES. POLYMERS ARE USEFUL IN PARTICULAR AS ION-EXCHANGING RESINS.

Description

The present invention relates to perfluoroallyl fluorosulfate and its

sultone, processes for their

  preparation and use of perfluorinated fluorosulfate

  allyl and its sultone in ion exchange resins and acid catalysts. In U.S. Patent No. 2,852,554, D C Engand discloses the reaction of hexafluoropropene with liquid anhydrous anhydride, freshly distilled, for

  give the sultone of 2-hydroxy-1-trifluoromethyl-

  1,242-trifluoroethanesulfonic acid (hexafluoropropene sultone) of the formula

CF 3 F CF F 2

  F 22 D England, M A Dietrich and R V Lindsey in "Reaction of Fluoroolefins with 503", J Amer Chem. Soc., 82, 6181 (1960) also report the reaction of hexafluoropropene (HFP) with sulfuric anhydride (503) distilled at 1000 ° C to give the HP sultone

CF 3 CF CF 2

  This reference (page 6184) also reports the reaction of hexafluoropropene with inhibited SO 3 at 60 ° C. to give an unidentified mixture, boiling point 50 ° -65 ° C., and a product with a high boiling point. which is probably a cyclic anhydride sulphonate sulfate of the formula CF 2

CF OF O

3 '

  02 N / A 2 MA Belaventsev, LL Mikheev, VM Pavlcv, GA Sokol'skii and IL Knunyants, Izv, Akad Nauk, USSR, Ser Khim 1972 (11), 2510-16 (Russ), English translation pages 2441-2445, describe the reaction of (CF 3) 2 C = CF 2 with 503 to 150-180 ° C to give, (c F 3) 2 CF 2 O 3 Q) 5, 02 SX So 2 o 2 S 2

(CF 3) 2 C = CFOSO 2 F 15%,

  and (CF 3) 2 C = CFOSO 3 O 502 F 24% GA Sokol'skii, MA Belaventsev and I L. Knunyants, Izv Akad, Nauk, USSR, Ser Khim 16 (9) 2020-2024 (Russ), English translation pages 1935-1938,

  describe the reaction of HI'P sultone with NOCI.

CF -CF CF

3 I-12 + NOC 1 -

  The present invention relates to the following pure compounds: perfluoroallyl fluorosulfate (CF 2 = CF-CF 20 SO 2 F) and its sultone

CF 2 CF-CF 20502 F

i 2

O SO 2

  These compounds have not been isolated previously or identi-

  from HFP and SO 3 reactions.

  The present invention also relates to processes for preparing perfluoroallyl fluorosulfate and its sultone by reacting hexafluoropropene (CF 3-CF = CF 2) with sulfur trioxide (SO 5) under anhydrous conditions in the presence of about 0.1 to about 5% by weight, based on sulfur dioxide, of a trivalent boron compound selected from oxide

  boric (B 205); boron trichloride (B C 13); the tri-

  boron fluoride (BF 3); tri (lower alkyl) borates (B (OR) 3); the alkyl group contains from 1 to 6 carbon atoms, for example trimethyl borate and triethyl borate; boron trioxychloride ((BOC 1) 3); and boron trioxyfluoride ((BOF) 5) at a temperature of about 0 to about 150 C for a time

  sufficient to produce perfluorinated fluorosulphate

  The preferred catalysts are B 203 BF 3 and B (OCH 3) 3 because of their effectiveness and availability. The sulfur trioxide used in this process may be commercially available liquid sulfur trioxide or it may be freshly distilled, uninhibited sulfuric anhydride. Commercial liquid sulfur trioxide (about 17 ° C. melting point) is sold in

  sealed glass ampoules and contains a "stabilized

  This inhibitor of the formation of solid polymeric sulfuric anhydride. For use in the preparation of the present invention, the SO 3 must be liquid at 200 ° C. The general process for preparing the compounds

  according to the present invention comprises the addition of anhy-

  sulfuric acid in a dry, thick-walled glass or metal tube having a corrosion-resistant lining such as a nickel alloy or stainless steel. The catalyst is added in an amount of from about 0.1 to about 5% by weight. sulfuric anhydride (preferably from about 0.3 to about 2.8% by weight) and hexafluoropropene is introduced under pressure or by condensation. The molar ratio of hexafluoropropene to sulfuric anhydride can vary within wide limits, but is

  preferably between about 1: 1 and about 5: 1.

  The reaction vessel is sealed and the reaction is conducted at temperatures between about 0 ° C and about 1500 ° C (preferably about 25 ° C to about 750 ° C) under the spontaneous pressure for a period of about one hour to one hour. Inert diluents may be used, but they do not offer any special advantage. Stirring is advantageous, but not essential Protic materials such as water, hydrochloric acid, fluorosulfonic acid, methanol, etc. , are harmful to the reaction and must

to be avoided.

  The duration of the reaction varies inversely with the temperature Although relatively low temperatures require a longer time for the maximum yield, they favor the production of

  fluorosulfate perfluoroallyl rather than hexafluoro-

  propene sultone Relatively high temperatures tend to reduce fluorosulfate yields

  perfluoroallyl and to increase the hexafluoro-

propene sultone.

  It has also been found that the fluorosulfate

  Fluoroallyl and its sultone can be prepared with

  certain quantities of sulfur dioxide from the non-distill

  Without the addition of a trivalent boron compound it is believed that the sulfuric anhydride batches which produce this result may contain an inhibitor which acts as a catalyst for this reaction. US Pat. No. 2,458,718 suggests that boron compounds

  have been used as inhibitors for sulphate

  furique. Possibilities of industrial use Perflucroallyl fluorosulfate according to the present invention can be homopolymerized or copolymerized

  with various fluoroethylenes such as vinyl fluoride

  vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene and tetrafluoroethylene.

  copolymers particularly pref Sr Gs are those of fluorescent

  vinylidene fluoride and perfluorinated fluorosulphate

  Generally, the copolymer will contain from about 1 to about 82, and preferably from about 5 to about

  % by weight of perfluoroallyl fluorosulfate, a fluoro

  roethylene constituting the remainder of the copolymer

  Mothers can be used as ion exchange resins and as acidic catalysts Apart from the sulfate group, the polymers according to the present invention are very stable to heat and chemically inert and thus do not interfere with the catalyzed reaction. They allow the use of corrosive reagents. or active ones and, moreover, make it possible to carry out the reaction catalyzed by an acid with

  high temperatures Hydrolysis of the fluorochemical polymer

  perfluoroallyl sulfate entralne the formation of carboxylic acid groups Thus, the polymer will contain mesh of the structure

-CF-CF 2

COH

  The advantage of this resin over a mineral acid is the easy separation of the reaction products from the catalyst, the possibility of regenerating the catalyst,

  the absence of waste mineral acid and the non-

corrosive catalyst.

  Perfluoroallyl fluorosulfate sultone

  can be transposed to form, at rest, fluorosulphonate

  P-fluorocarbonyl-O-fluorosulfonyltrifluoroethyl fate.

  This triacid fluoride product finds use

  as a catalyst for the polymerization of tetrahydrofuran.

  Perfluoroallyl fluorosulfate sultone can also be reacted with water to form trifluorovinylsulfonyl fluoride which is useful for preparing ion exchange resins and acid catalysts as described by HH Gibbs and RF Griffin in US Pat. The sultone can also be reacted with lower alkanols containing from 1 to 8 carbon atoms to form dialkyl fluorosulfonylfluoromalonates. Generally, the reaction is conducted between OC and 60 ° C.

  using atmospheric pressure.

  The products according to the present invention, their preparation and their use are illustrated by the

  following examples All temperatures are in C.

EXAMPLE 1

  Preparation of perfluoroallyl fluorosulfate and

  sultone of fluorosulfate of erfluoroallyl.

  A mixture of 10 cm of 503 commercial liquid containing an unknown inhibitor and 45 g of HFP is sealed in a Carius tube at the temperature of liquid nitrogen, mixed well at room temperature and heated at 150 ° C. for 4 hours. From two of these tubes, 26.5 g (25%) of sultone are obtained by distillation.

  of 2-hydroxy-1-trifluoromethyl-1,2,2-trifluoromethane-

  sulfonic acid, boiling point 45 C; 18.5 g (16%) of perfluoroallyl fluorosulfate, boiling point 59 ° C, and 16.4 g (21%) of the sultone of the latter, point

104 C boiling point

  Analysis: For perfluoroallyl fluorosulfate:

CF = CF-CF 20502 F

  IR: 5.55 t (C = C), 6.75 "(502) RMF: 46.1 ppm (triplet, J = 8.5 Hz, for doublets, J = 1.8 Hz, 1 F), - 74.0 ppm (doublets, J = 28.2 Hz, for doublets, J = 13.9 Hz, for doublets, J = 9.5 Hz, for doublets, J = 7.8 Hz, 2 F), -91 , 2 ppm (doublet, J = 50.0 Hz, for doublets, J = 40.5 Hz, for triplets, J = 7.8 Hz, AF), -104.7 ppm (doublet, J = 119.4 Hz , for doublets,

  J = 50.0 Hz, for doublets, J = 28.2 Hz), and -192.4 ppm.

  (doublet, J = 119.4 Hz, for doublets, J = 40.5 Hz, for triplets, J = 13, 9 Hz, for doublets, J = 1.8 Hz, 1 F).

  For perfluorinated fluorosulfate sultone

allyl: CF 2 F-CF 2 Oo 2 F

6.7 SO 2

'IR': 6.70:, 6.95 / l

2528 & 55

  RMF: 50.1 ppm (multiplet, 1 F), -78.0 ppm (multiplet, 2 F), -81.9 ppm, 83.9 ppm, -88.6 ppm, -90.6 ppm

  (AB model, 2 F), -152.4 ppm (multiplet, 1 F).

  Analysis: Calculated for C 3 F 65206: C, 11.62; F, 36.77 Found: C, 12.04; F, 37.81

EXAMPLE 2

  In each of four Carius tubes (capacity cm) was added 10 cm (19 g) of sulfur trioxide (stability with dimethyl phthalate) and 12 drops (0.12 g) of trimethyl borate, cooled with liquid nitrogen, reduced the diameter of the neck and evacuated Hexafluoropropene (45 g) is condensed in each tube, which is then sealed and heated, for melting and mixing of the contents. water bath at 55-60 ° C. Analysis of the product by gas chromatography (gc) indicates that the major product is perfluoroallyl fluorosulfate (FAFS) The combined product of the four tubes is subjected to fractional distillation to give a 45 g fraction, boiling mainly at 45 C, containing

  according to gc analysis 75% of sultone of 2-hydroxy-acid

  1-trifluoromethyl-1,2,2-trifluoroethanesulfonic acid (HFFS) and 25% FAFS; a fraction of 80 g, boiling mainly at 62 C, containing according to the 95% gc / FAFS analysis; and 44 g of uncharacterized products boiling at higher temperatures Compared with the charged SO 3, the total yield of IFFS is 14.8% o

  and the FAFS yield is 59.6%.

  For comparative purposes, the experiment above is repeated, except that no trimethyl borate catalyst is added. Product analysis by gc indicates that the major product is HIPS and no detectable.

from FAFS.

EXAMPLE:

  The following reactions in which distilled SO 3 is used are conducted in 2528 b 55 e tubes.

  metal of 1200 em 3 revs irtéririeurewmet ilastelloy.

  The efficiencies indicated are obtained by the rerdernerts in isolated products by conventional distillation techniques.

  The results are summarized in the following table, rt.

CF CF = CF 2.

  (moles) Catalyst Temperature and time

CF -CFCF OSC-F

  re dre Yi I c CE 3? F-o F yield, 5 c 3, t 5 nil

3.5 1.0

B (OCH 3) 3

3, 5 O '?

B (OCH 3) 5

3.5 2 BF 3

3.5 0.5 B 203

  600/22 hours, then 1000 / heures hours 250/3 days, then 1000/8 hours 250/5, days; 600/8 hours Qs; then 1000/2 hours 250/5 days; 600/8 hours; then 1000/2 hours 600/22 hours; The distilled 503 is then cooled to 0OC until it solidifies to a trimer, mp 1700, then melted at 0 to return to normal before reaction. (moles) o 2.7 2.0 2.1 ON 2.1

EXAMPLE 4

  A 1200 cm 3 tube coated internally with Hastelloy loaded with 240 g (3.0 moles) of SO 3, 3 g of BF and 525 g (3.5 moles) of hexafluoropropene is stirred briefly and then discarded. at 25 C for 3 days. After being heated at 100 C for 8 hours, the tube

  is cooled to 0 C while flushing the gases.

  The liquid products are collected and fractionated in a spinning column to give 61.5 g (9%) of crude sultone, boiling point

  46-60 C; 146.9 g (21%) of perfluorinated fluorosulfate

  allyl, boiling point 60 ° C (1 atm), -44 ° C (350 mm); and 155.4 g of mixture boiling at elevated temperatures, boiling point 49-56 ° C (50 mm) Analysis of the mixture by 19 F NMR indicated a mixture of three components: 82.9 g (18) of tetrafluoropropenyl -1,3-bis (fluorosulfate), 56.8 g (12 ao) of 2: 1 sultone (FSU 20 CF 2 C '-Cp 2) SO 2- o and 15.7 g of FSO 20 SO 205 02 F A central fraction of the fraction boiling at above high temperatures (64.6 g) is added to 150 cm 3 of 50 C ethyl ether and the mixture is shaken.

  overnight at room temperature

  gives 36, CF 5020 CF 2 CF = CFO 502 F pure, boiling point

  54-55 ° C (50 mm) IR (CC 14): 5.67 (C = C) and 6.72 f (O 502 F) 19 F NMR corresponds to a 1: 1.5 milgin of cis isomers / Analysis of F 50202 CCF 2 = CFOSO 2 F. Analysis: Calculated for C OF 60652 F, 36.76 Found: F, 56.74 (i EWPLE 5 A 1200 cm 3 Hastelloy tube loaded with 167 g (2, 09 moles) of distilled SO 2, 2 g of boron trifluoride and 525 g (5.5 moles) of hexafluoropropene are

  stirred at 25 ° C. for 5 days, then at 50 ° C. for 8 hours.

  The reaction mixture was cooled to 0 ° C., the gases were separated, and the reaction mixture was fractionated to give 21.9 g (5%) of crude hexafluoropropene sultone, boiling point. 30-610 ° C, and 2888.0 g

  (6 / o) perfluoroallyl fluorosulphate, boiling point

  61-63 C Perfluoroallyl fluorosulfate is identified by comparison of its IR spectrum with

  that of the corresponding product of Example 1.

EXAMPLE 6

  Copolymerization of perfluoroallyl fluorosulfate with vinylidene fluoride

  A mixture of 11 g of perfluorosulfate

  roallyl, 6.5 g of vinylidene fluoride and 50

  microliters of a catalyst solution containing approximately

  6% of perfluoropropionyl peroxide in 1,1,2-

  trichloro-1,2,2-trifluoroethane is sealed in a

  glass tube and it is rotated at room temperature

  For five days while cooling the tube. and by removing the boiling materials at low temperatures, 9.8 g of an elastomer which is soluble in acetone and also in

  Dimethylformamide Transparent films can

  may be cast from an acetone solution or press-formed from the solid polymer

  infrared spectrum indicates the presence of fluoro-

sulfate (-O 502 F).

  E MPLE 7: Copolymerization of perfluoroallyl fluorosulfate with vinylidene fluoride In an experiment similar to the previous one,

  but using 5.5 g of perfluorinated fluorosulfate

  allyl, 5.5 g of vinylidene fluoride and 50 microliters

  of the catalyst solution, 10.5 g of poly-

mother in 60 hours.

EXEMFLE 8:

  Copolymerization of perfluoroalkyl fluorosulfate with tetrafluoroethylene

  A perfusion of Lucrosulfide-perfluorinated

  roallyle, 9 tt, trafi 1 uoro't Ivl Lne, t die 50 micro-

  1 liter of the catalyst solution sealed in a 16 hour glass tube at room temperature gives 4 g of trifluric acid, fluorosulphide, 11 ucrc '1 lj 1 ye and 1 5 ,? dc, aic volatile. EXAMPLE 9 Copolymerization of fluorosulfide of pertoroalkyl with vinyl fluoride

  A mixture of 11 g perfluorosulfate fluorosulfate

  allyl, 4.5 g of vinyl fluoride and dI; O micro

  liters of the catalyst solution sealed in a tube

  in glass at the amibiante temperature don-ne 51, g of a copo-

  Dark perfluoroallyl fluorosulphur

  vinyl chloride and 4 g of volatile matter.

EX 2, iPLE 10

  Transposition of the fluorosulfide sultone of perfliacro-

  allyl to fluorosulphate of 1 B-fluorocarbonyl-1-fluorophenyl

  sulfonylitrifluoroethyl CF CF-CF O WG 1 'F 1 C j 2 2 0 302 F i'r A sample of the same sample, it was abandoned for several months in a flaz-con (, Tl glass is redistil 1 e Apres distillaption of sul-torne

  recovered (point of Jhu 11 it Vicn <37 O under, 110 rj lec pro-

  distilled trichlorosulfate, fluorocarbon fluorosulfate, and trifluorocarbon (40% strength);

AV 7 ALYSE

  LF 51.7 pp (obese), p (triplet, J = c, 42 Hz, I), δ, p (d = J = 2.5 Hz, 1 for trlp, 17, S ( z I) f-, pm (doublet, J = 8.2 Hz, for doublet, J = 7.8 Hz, for

  doublet, J = 7.5 Hz, 2 F), -155.7 ppm (doublet, J -

  J = 22.5 Hz for triplet, J = 7.5 Hz, for doublet,

J = 5.2 Hz, IF).

EXAMPLE 11

  Reaction of perfluorinated fluorosulfate sultone

  ally with water to form trifluoride

fluorovinylsulfonyle

F 2 CF-CF 2 OSOF H 2 02 F

\ 2/2

C + C 02

O-802 FX-F CF 20502 F

H 502 F

CF 2 = CF-502 F + HOSO 2 F

F / "CF 0802 F

2 2

  P-Hydro-p Fluorosulphate Trifluoro- Fluoride

  fluorosulfonyltrifluoroethyl vinylsulfonyl The above sultone (62 g, 0.2 moles) was stirred by cooling to maintain the temperature in the range of -10 to + 20 ° C while adding dropwise 14.4 cm 3 of H 2 O. The mixture is heated under

  vacuum and condense the product in a carbon trap.

  ice We distil the material present in the trap

  to obtain 16 g (46%) of trifluorovinyl fluoride

  sulfonyl, boiling point 53 ° C, and 9.6 g (18%) of 3-hydroxy-fluorosulfonyltrifluoroethyl fluorosulfate,

boiling point 74 ° C / 70 mm.

Analysis

  For p-hydro-p-fluorosulphonosulphate

  fonyltrifluoroethyl IR: 6.70, 6.86 (502) RMP: 5.64 ppm (doublet J = 44, 5 Hz for triplets, J = 6.1 Hz for doublet, J = 2.5 Hz, 1 H) FMR : 49.1 ppm (triplet,

  J = 8.4 Hz for doublet, J = 1.0 Hz, 1 F), 52.6 ppm.

  (triplet, J = 9.7 Hz, for doublet, J = 6.7 Hz, for doublet, J = 2.5 Hz, 1 F), -77.9 ppm (multiplet, 2 F) and -190.5 ppm (doublet, J = 44.5 Hz, for triplet, J 12.3 Hz, for doublets, J = 6.7 Hz, for doublets, J = 1, 0 Hz, 1 F). Analysis: Calculated for C HF 520:

2,525

  C, 9.10; H, 0.58; F, 55.98; S, 24.29

Find:

  C, 9.30; H, 0.40; F, 55.4; S, 25.20.

  For trifluorovinylsulfonyl fluoride:

  IR: 5.70 / (C = C), 6.80 / 8 (502) F: 61.2 ppm.

  (doublet, J = 13.8 Hz, for doublet, J = 5.3 Hz for doublet, J = 4.1 Hz, IF), -88.5 ppm (doublet, J = 43.0 Hz, for doublet, J = 17.0 Hz, for doublet, J = 13.8 Hz, 1 F), -90.9 ppm (doublet, J = 121.8 Hz, for doublet, J = 17.0 Hz, for doublet, J = 4.1 Hz, IF) and -180.9 ppm (doublet, J = 121.8 Hz, for doublet, J = 43.0 Hz,

for doublet, J = 5.3 Hz, 1 F).

Analysis: Calculated for C F 45 O 2:

24 2

C, 14.65; F, 46.34; 3, 19.55

  Found: C, 14.60; F, 45.91; S, 17.29

REVA DICAT IONS

  1 The use of perfluorosulfate

  roallyl CF 2 = CF-CF 20502 F for the preparation of a homo-

  polymer containing mesh structure

--CF, -CF-

2 I

CF 205 O 2 F

  2 The use of perfluorosulfate

  roallyl CF 2 = CF-CF 20 SO 2 F for the preparation of copoly-

  mothers with fluoroethylenes, in which fluorine

  perfluoroallyl sulphate is present in a proportion of 1 to 80%

in weight.

  The use of roallyl fluorosulfate according to claim 2, characterized

  fluoroethylene is vinylidene fluoride.

  The use of roallyl fluorosulfate according to claim 2, characterized

  fluoroethylene is tetrafluoroethylene.

  The use of roallyl fluorosulfate according to claim 2, characterized

  Fluoroethylene is vinyl fluoride.

perfluorinated

in that

perfluorinated

in that

perfluorinated

in that