JPS6238362B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for making perfluoroallyl fluorosulfate homopolymers or copolymers. Specifically, according to the invention, the formula A homopolymer having repeating units of or repeating units of formula and formula [Here, R ₁ to _{R 4} each independently represent hydrogen or fluorine, provided that at least one of R ₁ to _{R 4} represents fluorine] In producing a copolymer having a repeating unit of , perfluoroallylfluorosulfate is contacted with a catalyst, or perfluoroarylfluorosulfate and perfluoroarylfluorosulfate of the formula ' [Here, R ₁ to _{R 4} have the same meanings as above] A production method is provided in which the following monomers are brought into contact in the presence of a catalyst. The details of the present invention will be explained below, including the method for producing the monomer perfluoroallyl fluorosulfate and its sultone. DCEngland
No. 2,852,554, hexafluoropropene is reacted with freshly distilled liquid anhydrous sulfur trioxide to form the formula 2-hydroxy-1-trifluoromethyl-
A method for producing 1,2,2-trifluoroethanesulfonic acid sultone (hexafluoropropene sultone) is described. Journal of the American Chemical Society (J.Am.Chem.Soc.), Vol. 82, p. 6181, by DC England, MADietrich, and RVLindsey. (1960), "Reaction of fluoroolefins with SO ₃ ", states that when hexafluoropropene (HFP) is reacted with freshly distilled sulfur trioxide at 100°C, the sultone of HFP is formed. It is stated that this can be obtained. of this literature
Page 6184 also states that when hexafluoropropene is reacted with SO ₃ containing an inhibitor at 60°C, a mixture of unknown structure with a boiling point of 50-65°C and possibly a compound of the formula It has been reported that a high boiling product, believed to be a cyclic sulfonate-sulfate anhydride, is obtained. M.A. Belaventiev (MA
Belaventsev), El El Mikheyev (LL
Mikheev), V.M. Pavlov (VM
Pavlov), G.A.
Sokol′skii) and ILKnunyants (Izv.Akad.Nauk.SSSR.Ser.
(CF ₃ ) ₂ C=
When CF ₂ and SO ₃ are reacted at 150-180℃, It is stated that this can be obtained. G. A. Sokolisky, M. A. Beraventiev and E. L. Kuniyants, above-mentioned Izveestia Magazine 1967 (No. 9) 2020-2024
pages (Russian version), pages 1935-1938 (English version)
Reaction of reacting HFP sultone with NOCI is listed. Perfluoroallyl fluorosulfate (CF ₂ = CF−CF ₂ OSO ₂ F) and its sultone has never been isolated or identified from the reaction between HFP and _SO3 . Boron oxide (B ₂ O ₃ ); boron trichloride (BCl ₃ ); boron trifluoride (BF ₃ ); tri(lower alkyl)borate (B(OR) ₃ ) whose alkyl group has 1 to 6 carbon atoms, e.g. Trimethylborate and triethylborate;
A boron compound selected from _{the group consisting of boron trioxychloride ((BOCl) 3 )} ;
Hexafluoropropene ( _CF3 -CF= _CF2 ) is treated with sulfur trioxide (CF3-CF=CF2) under anhydrous conditions in the presence of ~0.5% by weight and at a temperature of about 0 to about 150<0>C for a sufficient time to form perfluoroallyl fluorosulfate. Perfluoroallyl fluorosulfate and its sultone can be produced by reacting with SO ₃ ). Preferred catalysts are B ₂ O ₃ , BF ₃ , and B(OCH ₃ ) ₃ due to their efficiency and availability.
It is. The sulfur trioxide can be commercially available liquid sulfur trioxide or freshly distilled inhibitor-free sulfur trioxide. Commercially available liquid sulfur trioxide (melting point ~17°C) is available in sealed glass ampoules and contains ``stabilizers'' that inhibit the formation of solid, polymerized sulfur trioxide. For use in preparing compounds of the invention, _SO3 must be liquid at 20°C. A common method for making perfluoroallyl fluorosulfate is to add sulfur trioxide to a dry, thick-walled glass tube or metal tube with a corrosion-resistant liner, such as a nickel alloy or stainless steel liner. Catalyst is added in an amount of about 0.1 to about 5 weight percent (preferably about 0.3 to about 28 weight percent) based on sulfur trioxide, and the hexafluoropropene is injected or condensed. The molar ratio of hexafluoropropene to sulfur trioxide can vary widely, but is preferably from about 1:1 to about 5:1. The reaction vessel is sealed and kept at about 0°C to about 150°C (preferably about 25°C) for about 1 hour to about 1 week under autogenous pressure.
The reaction is carried out at a temperature of ~75°C). Inert diluents can be used but have no particular advantage. Stirring is preferred, but not essential. Proton-containing materials such as water, hydrogen chloride, fluorosulfonic acid, and methanol are harmful to this reaction;
This must be avoided. Reaction time is inversely related to temperature. Although a long time is required at low temperatures to obtain the maximum yield, perfluoroallyl fluorosulfate is more likely to form as a product than hexafluoropropane sultone at low temperatures. Higher temperatures tend to decrease the yield of perfluoroallyl fluorosulfate and increase the content of hexafluoropropane sultone. It has been found that perfluoroallyl fluorosulfate and its sultones can be prepared using undistilled commercially available sulfur trioxide without the addition of trivalent boron compounds. It is believed that the batches of sulfur trioxide that give these results contain a polymerization inhibitor that catalyzes this reaction. US Pat. No. 2,458,718 suggests that boron compounds are used as polymerization inhibitors for sulfur trioxide. Perfluoroallyl fluorosulfate can be homopolymerized or copolymerized with various fluoroethylenes, such as vinylidene fluoride, vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, and tetrafluoroethylene. can. A particularly preferred copolymer is a copolymer with vinylidene fluoride and perfluoroallyl fluorosulfate. Generally, the copolymer is about 1
to about 80%, preferably about 5 to about 50% by weight perfluoroallyl fluorosulfate, with the balance being fluoroethylene. This polymer can be used as an ion exchange resin or an acid catalyst. Other than the sulfate groups, the polymers of the present invention are very temperature stable, chemically inert, and do not interfere with catalytic reactions. Therefore, corrosive or reactive reagents can be used and acid-catalyzed reactions can be performed at elevated temperatures. Hydrolysis of perfluoroallyl fluorosulfate polymers produces carboxylic acid groups. Therefore, this polymer has the structural formula contains repeating units. The advantages of this resin over mineral acids are that the reaction products can be easily separated from the catalyst, the catalyst can be regenerated, no mineral acid waste is produced, and the catalyst is not corrosive. The manufacturing method of the present invention will be explained using the following examples and reference examples. Reference Example 1 Method for producing perfluoroallyl fluorosulfate and perfluoroallyl fluorosulfate sultone. Commercial liquid SO ₃ containing unknown polymerization inhibitor 10
ml and 45 g of HFP are sealed in a Carius tube at liquid nitrogen temperature, mixed thoroughly at room temperature, and heated to 150° C. for 4 hours. From these two tubes, 26.5 g (23%) of 2-hydroxy-1-trifluoromethyl-1,2,2-trifluoroethanesulfonic acid sultone with a boiling point of 45°; perfluorinated with a boiling point of 59° Allyl fluorosulfate 18.5
g (16%); and the latter sultone with a boiling point of 104°
16.4g (21%) was obtained. Analysis Regarding perfluoroallyl sulfate; CF=CF− _CF2OSO2FIR :5.55μ( _C =C),
6.75μ( _SO2 ). FMR: 46.1ppm (triple line, J=8.5Hz, double line, J=1.8Hz, 1F), -74.0ppm (double line, J=
28.2Hz, double line, J=13.9Hz, double line, J=9.5
Hz, double line, J=7.8Hz, 2F), -91.2ppm (double line, J=50.0Hz, double line, J=40.5Hz, triple line,
J=7.8Hz, 1F), -104.7ppm (double line, J=
119.4Hz, double line, J=50.0Hz, double line, J=28.2
Hz), -192.4ppm (double line, J=119.4Hz, double line, J=40.5Hz, triple line, J=13.9Hz, double line,
J = 1.8Hz, 1F). Regarding perfluoroallyl fluorosulfate sultone; IR: 6.70μ, 6.93μ FMR: 50.1ppm (multiplet, 1F), −78.0ppm
(Multiplet, 2F), −81.9ppm, −83.9ppm, −
88.6ppm, −90.6ppm (AB pattern, 2F), −
152.4ppm (multiplet, 1F). C ₃ F ₆ S ₂ O ₆ Calculated value C, 11.62; F, 36.77 Detected value C, 12.04; F, 37.81 Reference example 2 10 ml in each of 4 Carius tubes (volume 150 ml)
(19 g) of SO ₃ (stabilized with dimethyl phthalate)
and 12 drops (0.12g) of trimethylborate,
Cool with liquid nitrogen, close the pot and draw a vacuum. Condensate hexafluoropropene (45 g) into each chamber, seal it, heat to melt, and mix the contents. Heat this in a water bath at 55-60° for 14 hours. Gas chromatography (GC) analysis revealed that the main product was perfluoroallyl fluorosulfate (FAFS). The products of the four tubes were combined and fractionally distilled to yield 75% 2-hydroxy-1-trifluoromethyl-1,2,2-trifluoroethanesulfonic acid sultone (HFPS) as analyzed by GC. and 25%
There were obtained 45 g of a product with a main boiling point of 45°, which is FAFS; 80 g of a product with a main boiling point of 62°, which was analyzed by GC as 95% FAFS; and 44 g of unidentified high-boiling components. The overall yield of HFPS with respect to the SO ₃ used was 14.8
%, and that of FAFS was 39.6%. As a control, the above experiment was repeated without the trimethylborate catalyst. As a result of product analysis by GC, the main product was HFPS, and FAFS was not detected. Reference Example 3 The following reaction was carried out using distilled SO ₃ in a 1200 ml metal tube lined with Hastalloy. The yields shown are based on product isolated by conventional distillation methods.
The results are summarized in the table below.

[Table] Reference example 4 240ml in a 1200ml Hastaloy lined tube
g (3.0 mol) SO ₃ , 3 g BF ₃ , and 525 g
(3.5 mol) of hexafluoropropene is stirred briefly and then left at 25° C. for 3 days. 100
After heating for 8 hours at 0.degree. C., the tube is cooled to 0.degree. C. while degassing. The liquid product was collected and fractionated in a rotating band distillation column to produce 61.3 g (9%) of crude sultone with a boiling point of 46-60°C; perfluoroallyl with a boiling point of 60° (1 atm) and -44° (350 mm). Fluorosulfate 146.9g (21%); and boiling point 49-56° (50
155.4 g of a high boiling point mixture of 1 mm) was obtained. Analysis of this mixture by ¹⁹ FNMR revealed that it was a ternary mixture, with tetrafluoropropenyl-1,3-
Bis(fluorosulfate) 82.9g (18%),
2:1 sulton

[Formula] 56.8g (12%), and FSO ₂ OSO ₂ OSO ₂ F15.7g. The middle distillate (64.6 g) of the above high boiling point fraction was heated at 5°.
150ml of diethyl ether was added and the mixture was stirred overnight at room temperature. As a result of fractionation, pure
FSO ₂ OCF ₂ CF=CFOSO ₂ F [boiling point 54~55゜(50
mm)] 36.0 g was obtained. IR ( _CCl4 ): 5.67μ (C=
C), 6.72μ ( _OSO2F ). ¹⁹ FNMR:
FSO ₂ OCF ₂ CF ₂ = corresponds to a 1:1.3 mixture of cis/trans isomers of CFOSO ₂ F. Analytical value C ₃ F ₆ O ₆ S ₂ : Calculated value F, 36.76 Detected value F, 36.74 Reference example 5 167 g (2.09 moles) of distilled SO ₃ , 2 g of BF ₃ , and 525 g (3.5 moles) in a 1200 ml Hastaloy tube. of hexafluoropropene and stirred at 25° for 5 days, then at 60° for 8 hours, then at 100° for 2 hours. This tube was cooled to 0°, degassed,
The reaction mixture was fractionated to yield 21.9 g (5%) of crude hexafluoropropene sultone with a boiling point of 30-61° and 288.0 g (60%) of perfluoroallyl fluorosulfate with a boiling point of 61-63°. Perfluoroallyl fluorosulfate was identified by comparison with the IR spectrum of the corresponding product of Example 1. Example 1 Copolymerization of perfluoroallyl fluorosulfate and vinylidene fluoride. 11 g perfluoroallyl fluorosulfate, 6.5 g vinylidene fluoride, and about 6% perfluoropropionyl peroxide in 1,1,
A mixture of 50 μ of the catalyst solution in 2-trichloro-1,2,2-trifluoroethane is sealed in a glass tube and rotated for 5 days at room temperature. After cooling, opening, and removing low-boiling components, 9.8 g of elastomer soluble in acetone and dimethylformamide was recovered. Transparent films could be obtained by casting from an acetone solution or by pressing the solid polymer. Its infrared absorption showed the presence of fluorosulfate groups ( _-SO2F ). Example 2 Copolymerization of perfluoroallyl fluorosulfate and vinylidene fluoride. An experiment similar to the above was carried out using 5.5 g of perfluoroallyl fluorosulfate, 5.5 g of vinylidene fluoride and 50μ of the catalyst solution.
10.5 g of polymer was obtained. Example 3 Copolymerization of perfluoroallyl fluorosulfate and tetrafluoroethylene. 11 g of perfluoroallyl fluorosulfate, 9 g of tetrafluoroethylene and 50μ of catalyst solution were sealed in a glass tube at room temperature for 16 hours, and 4 g of copolymer of tetrafluoroethylene and perfluoroallyl fluorosulfate and 13.5 volatile components were added.
I got g. Example 4 Copolymerization of perfluoroallyl fluorosulfate and vinyl fluoride. 11 g of perfluoroallyl fluorosulfate, 4.5 g of vinyl fluoride, and 50μ of the catalyst solution were sealed in a glass tube at room temperature, 5.2 g of the dark copolymer of perfluoroallyl fluorosulfate and vinyl fluoride, and evaporated. 4 g of ingredient was obtained.

Claims (1)

[Claims] 1 formula A homopolymer having repeating units of or repeating units of formula and formula [Here, R ₁ to _{R 4} each independently represent hydrogen or fluorine, provided that at least one of R ₁ to _{R 4} represents fluorine] In producing a copolymer having a repeating unit of , perfluoroallyl fluorosulfate is contacted with a catalyst or perfluoroallyl fluorosulfate and the formula ' [Here, R ₁ to _{R 4} have the same meanings as above] A production method comprising contacting the monomer of [Here, R 1 to R 4 have the same meanings as above] in the presence of a catalyst. 2. (a) a copolymer is produced, (b) the monomer of formula ' is selected from tetrafluoroethylene, vinyl fluoride and vinylidene fluoride, (c) the catalyst is perfluoropropionyl peroxide, and (d) A method according to claim 1, wherein the copolymer has from 1 to 80% by weight of repeating units of the formula.