Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2002-05-01
2004-07-06
Cheung, William K (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S551000, C524S609000, C524S805000, C524S834000
Reexamination Certificate
active
06759477
ABSTRACT:
FIELD OF THE INVENTION
This invention is directed to a method for preparing imides from compounds having a sulfonyl fluoride functional group. The imides so prepared are useful in a variety of catalytic and electrochemical applications.
BACKGROUND OF THE INVENTION
Compounds having a sulfonyl fluoride functional group are well known in the art. In particular, vinyl ethers and olefins having a fluorosulfonyl fluoride group have been found to be particularly useful as monomers for copolymerization with tetrafluoroethylene, ethylene, vinylidene fluoride and other olefinic and fluoroolefinic monomers to form polymers which, upon hydrolysis are converted to highly useful ionomers. One area of important use for ionomers so formed is in the area of lithium batteries. See for example Connolly et all U.S. Pat. No. 3,282,875 and commonly assigned Ser. No. 09/023,244 U.S. Pat. No. 6,025,092 and Ser. No. 09/061,132 U.S. Pat. No. 6,100,324.
It is also known to prepare imides from compounds having sulfonyl fluoride functionality particularly fluorinated organic sulfonyl imides are known in the art. For example, DesMarteau, U.S. Pat. No. 5,463,005, discloses substituted perfluoro-olefins of the formula
where X═CH or N, Z═H, K, Na, or Group I or II metal, R=one or more fluorocarbon groups including fluorocarbon ethers and/or sulfonyl groups and/or perfluoro non-oxy acid groups, Y=perfluoroal or F, and m=0 or 1.
Xue, Ph.D. thesis, Clemson University, 1996, discloses the formation of the monomer
CF
2
═CF—OCF
2
CF
2
SO
2
N(Na)SO
2
CF
3
by reaction of CF
2
═CF—OCF
2
CF
2
SO
2
Cl with CF
3
SO
2
NHNa in the presence of Na
2
CO
3
in acetonitrile. However, Xue's method is not applicable to the sulfonyl fluoride species without first protecting the double bond.
Further disclosed by Xue, op.cit, is CF
3
SO
2
NNa
2
made by combining CF
3
SO
2
NHNa and NaH in THF and reacting for four hours at room temperature. The inventors hereof have determined that Xue's method of preparation provides a conversion of less than 10% from CF
3
SO
2
NHNa to CF
3
SO
2
NNa
2
. No method of separation is provided, nor is any method provided for preparing the CF
3
SO
2
NNa
2
at higher yield. Thus no means is provided for producing CF
3
SO
2
NNa
2
in a highly purified state. Xue suggests that CF
3
SO
2
NNa
2
can be reacted with a cyclic sulfone of the formula:
to produce the vinyl ether monomer, CF
2
═CF—OCF
2
CF
2
SO
2
N(Na)SO
2
CF
3
. Also disclosed by Xue is a reaction between CF
2
═CFOCF
2
CF
2
SO
2
F and CF
3
SO
2
NHNa to produce an unusable complex mixture of products. Xue makes no suggestion that CF
3
SO
2
NNa
2
is effective at converting sulfonyl fluoride containing compounds to imides.
MeuBdoerffer et al., Chemiker Zeitung, 96. Jahrgang (1972) No. 10, 582-583 discloses a method for synthesizing RSO
2
NH
2
wherein R is perfluoroalkyl.
Feiring et al., WO 9945048(A1), provides a method for imidizing fluorinated vinyl ether monomers containing a sulfonyl fluoride group by first protecting the double bond and then converting the sulfonyl fluoride into an imide.
Armand et al, EPO 0 850 920 A2, discloses a method for imidizing sulfonyl fluoride and chloride species containing aromatic rings.
SUMMARY OF THE INVENTION
The present invention provides for a process comprising: Contacting, in a liquid dispersion or solution, a composition comprising a sulfonyl amide salt represented by the formula:
(R
2
SO
2
NM
b
)
3-b
M′
c
(III)
wherein R
2
is aryl, fluoro-aryl, or XCF
2
— where X is H, halogen, fluorinated or non-fluorinated linear or cyclic alkyl radicals having 1-10 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 an alkaline earth when b is 1 or an alkali metal when b is 2 and c=0, and M is alkali metal when b=1 and c=1, with the proviso that c is not equal to 1 when b=2 with
a non-polymeric sulfonyl fluoride composition represented by the formula R
1
(SO
2
F)
m
(IV)
wherein m=1 or 2, where, when m=1, R
1
is a fluorinated or non-fluorinated, saturated or unsaturated hydrocarbyl radical, except perfluoroolefin, having 1-12 carbons optionally substituted by one or more ether oxygens, or tertiary amino; or, when m=2, R
1
is a fluorinated or non-fluorinated, saturated or unsaturated hydrocarbylene, except perfluoroalylene, radical having 1-12 carbons optionally substituted by one or more ether oxygens;
or with a polymeric sulfonyl fluoride composition comprising monomer units represented by the formula
—[CZ
2
CZ(R
3
SO
2
F)]— (V)
wherein R
3
is a diradical selected from the group consisting of fluorinated or non-fluorinated allylene, including oxyalkylene or fluorooxyalkylene, but not perfluoroalkylene, and each Z is independently hydrogen or halogen, and the Zs need not be the same; and,
causing them to react to form a non-polymeric imide composition represented by the formula:
wherein y=1 or 2, M is an alkali when y is 1 or an alkaline earth metal when y is 2, m=1 or 2, where, when m=1, R
1
is a fluorinated or non-fluorinated, saturated or unsaturated hydrocarbyl radical, except perfluoroolefin, having 1-12 carbons optionally substituted by one or more ether oxygens, or tertiary amino; or, where m=2, R
1
is a fluorinated or non-fluorinated, saturated or unsaturated hydrocarbylene, except perfluoroalkylene, radical having 1-12 carbons optionally substituted by one or more ether oxygens, with the proviso that when y=2 and m=2, M may represent a combination of alkali and alkaline earth metals;
or, in the alternative, a polymeric imide composition comprising monomer units represented by the formula:
wherein y=1 or 2; R
3
is a diradical selected from the group consisting of fluorinated or non-fluorinated alkylene, including oxyalkylene or fluorooxyalkylene, each Z is independently hydrogen or halogen, wherein the Z's need not be the same; R
2
is aryl, fluoro-aryl, or XCF
2
—where X is H, halogen, fluorinated or non-fluorinated linear or cyclic alkyl radicals having 1-10 carbons, optionally substituted by one or more ether oxygens; M is an alkali when y is 1 or an alkaline earth metal when y is 2.
As used herein, the term “reacting” is intended to mean allowing or to allow 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: 3282875 (1966-11-01), Connolly et al.
patent: 5463005 (1995-10-01), Desmarteau
patent: 0850920 (1997-12-01), None
patent: WO 9945048 (1999-09-01), None
Von Johann N. Meubdoerffer und Hans Niederptim, Bisperfluoralkansulfonylimide, Chemiker-Zeitung, (1972) pp. 582-583, vol. 96, Jahrgang.
Cheung William K
E. I. du Pont de Nemours and Company
LandOfFree
Method for preparing imides from sulfonyl fluorides does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Method for preparing imides from sulfonyl fluorides, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Method for preparing imides from sulfonyl fluorides will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3211412