Method for preparing fluorosulfonyl imide monomer

Details Method for preparing fluorosulfonyl imide monomer Method for preparing fluorosulfonyl imide monomer

2002-06-14

2004-09-14

O'Sullivan, Peter (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

Reexamination Certificate

active

06790990

ABSTRACT:

FIELD OF THE INVENTION
The present invention is directed to a method for the preparation of a fluorosulfonyl imide monomer useful for forming ionomers. Such ionomers are useful in electrochemical applications such as batteries, fuel cells, electrolysis cells, ion exchange membranes, sensors, electrochemical capacitors, strong acid catalysts, and modified electrodes.
BACKGROUND OF THE INVENTION
Monomers represented by the formula
CF
2
=CFOCF
2
CF
2
SO
2
F  (I)
are employed by Ezzell et al., U.S. Pat. No. 4,940,525 to form copolymers with TFE followed by hydrolysis to the ionomer form. Ionomers of the type disclosed by Ezzell are suitable for a variety of electrochemical applications including the chloralkali process.
Putnam et al., U.S. Pat. No. 3,301,893, or in the alternative Resnick, U.S. Pat. No. 3,560,568, discloses a process for preparing CF
2
=CFOCF
2
CF
2
SO
2
F by pyrolysis of FSO
2
CF
2
CF
2
OCFCF
3
COONa. Resnick, op.cit., forms a cyclic sulfone of the formula
by pyrolyzing the FSO
2
CF
2
CF
2
OCFCF
3
C(O)F of Putnam in the presence of Na
2
CO
3
. Resnick then reacts the cyclic sulfone (II) with sodium methoxide to form CF
2
=CFOCF
2
CF
2
SO
3
Na which is then converted through a series of steps to the monomer (I) followed by copolymerization with TFE and subsequent hydrolysis to the ionomer form.
Putnam discloses the generalized reaction scheme
where X is CF
3
- or F, and R
f
is F or perfluoroalkyl.
Xue, Ph.D. Thesis, Clemson University, 1996, shows that a composition containing CF
3
SO
2
NNa
2
when reacted with the cyclic sulfone (II), provides a 4% yield of CF
2
=CFOCF
2
CF
2
SO
2
N(Na)SO
2
CF
3
(III) amidst a much larger yield of saturated species. Xue provides no method for achieving a higher yield of (III). There is no teaching in Xue in regard to the concentration of CF
3
SO
2
NNa
2
in the reaction mixture, nor as to the relationship between yield of (III) and the concentration of the CF
3
SO
2
NNa
2
.
DesMarteau, U.S. Pat. No. 5,463,005, discloses the copolymer of (III) with tetrafluoroethylene to form an ionomer. Feiring et al., WO9945048(A1), disclose the copolymer of (III) with vinylidene fluoride to form a lithium ionomer.
SUMMARY OF THE INVENTION
The present invention is a process for forming, at a yield greater than 50 mol-%, a monomeric composition represented by the formula
(CF
2
=CFOCF
2
CFXSO
2
N(M)SO
2
R
y
  (IV)
wherein X is F or perfluoroalkyl having 1-4 carbons optionally substituted by ether oxygen, M is an alkali or alkaline earth metal when y is respectively 1 or 2, R is aryl, fluoro-aryl, or XCF
2
- where X is H, halogen, fluorinated or non-fluorinated linear alkyl having 1-10 carbons or cyclic alkyl having 3-10 carbons, optionally substituted by one or more ether oxygens;
the process comprising:
contacting in an inert atmosphere a cyclic sulfone represented by the structure
wherein X is F or perfluoroalkyl having 1-4 carbons optionally substituted by ether oxygen with a composition sulfonyl amide salts of which said salts at least 50 mol-% are sulfonyl amide salts represented by the formula
(RSO
2
NM
b
)
3-b
M′
c
  (V)
wherein R is aryl, fluoro-aryl, or XCF
2
- where X is H, halogen, fluorinated or non-fluorinated linear alkyl radicals having 1-10
where R is aryl, fluoro-aryl, or XCF
2
- where X is H, halogen, fluorinated or non-fluorinated linear alkyl radicals having 1-10 carbons or cyclic alkyl radicals having 3-10 carbons, optionally substituted by one or more ether oxygens, M′ is an alkaline earth metal, b=1 or 2, c=0 or 1, M is alkaline earth or alkali metal when b is 1 or 2 respectively and c=0, and M is alkali metal when b=1 and c=1, with the proviso that c≠1 when b=2, thereby forming a ring-opening reaction mixture; reacting said ring-opening reaction mixture at a temperature in the range of 0 to 67° C.
As used herein, the term “reacting” is intended to mean allowing at least two components in a reaction mixture to react to form at least one product. “Reacting” may optionally include stirring and/or heating or cooling.


REFERENCES:
patent: 3301893 (1967-01-01), Putnam et al.
patent: 3560568 (1971-02-01), Resnick
patent: 4940525 (1990-07-01), Ezzell et al.
patent: 5463005 (1995-10-01), Desmarteau

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