Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2003-05-12
2004-01-27
O'Sullivan, Peter (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C562S011000, C562S012000, C562S065000, C562S430000, C525S333500, C568S028000
Reexamination Certificate
active
06683209
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to the synthesis of aromatic-irnide and aromatic-methylidynetrissulfonyl species. The synthesis proceeds by reaction of aromatic species, including aromatic polymers, with a reactant according to the formula: (X—SO
2
—)
m
—QH—(—SO
2
—R
1
)
n
; wherein Q is C or N and X is a halogen. The present invention additionally relates to compounds according to the formula: (Ar—SO
2
—)
m
—QH—(—SO
2
—R
1
)
n
wherein R
1
comprises a highly acidic group selected from sulfonic acid, carboxylic acid and phosphonic acid, which may be particularly useful as electrolytes.
BACKGROUND OF THE INVENTION
U.S. Pat No. 6,090,895 discloses crosslinked polymers having imide crosslinking groups and methods of crosslinking polymers to form imide crosslinking groups. These crosslinked polymers may be useful as polymer electrolyte membranes (PEM's) in fuel cells. The reference discloses methods of making imides by reaction of acid halides with amides, including aromatic acid halides and aromatic amides. The acid halides may be formed by haloacidification, e.g., chlorosulfonation, of aromatic species.
U.S. Pat No. 6,063,522 discloses electrolytes for use in electrochemical cells that include imide and methide conductive salts. The reference also discloses methods of making imides by reaction of acid halides with amides.
U.S. Pat. No. 4,505,997 discloses syntheses of imides by reaction of sulfonate and sulfonic anhydride species with urea. The reference discloses electrolytes comprising imide functional groups.
U.S. Pat. No. 5,652,072 discloses syntheses of imides by reaction of sulfonyl halide species with ammonia or with amide species. The reference discloses electrolytes comprising imide functional groups.
U.S. Pat. No. 5,072,040 discloses syntheses of imides by reaction of sulfonyl halide species with nitride species. The reference suggests the use of imide functional species in electrolytes.
U.S. Pat. No. 5,514,493 discloses syntheses of imides by reaction of sulfonyl halide species with ammonia or with amide species. The reference discloses electrolytes comprising imide functional groups.
U.S. Pat. No. 5,463,005 discloses perfluorinated monomers and polymers comprising sulfonyl and carbonyl imide groups for use as solid polymer electolytes. The reference discloses a synthesis of imides by reaction of amides with hexamethyldisilazine followed by reaction with a sulfonyl fluoride.
Argyropoulos & Lenk, “Condensation Products from Imidobis(sulfuryl Chloride),”
J. Ap. Polym. Sci.
v. 26, pp. 3073-3084 (1981), discloses reactions of imidobis(sulfuryl chloride).
SUMMARY OF THE INVENTION
Briefly, the present invention provides a method of making aromatic-imide and aromatic-methylidynetrissulfonyl species by reaction of aromatic species with a reactant according to formula (I):
(X—SO
2
—)
m
—QH—(—SO
2
—R
1
)
n
(I)
wherein Q is C or N; wherein each X is independently selected from the group consisting of halogens, typically F or Cl; wherein each R
1
is independently selected from the group consisting of aliphatic and aromatic groups, which may or may not be saturated, unsaturated, straight-chain, branched, cyclic, heteroatomic, polymeric, halogenated, fluorinated or substituted; wherein m is greater than 0; wherein m+n=2 when Q is N; and wherein in m+n=3 when Q is C. Ar may be derived from an aromatic polymeric compound.
In another aspect, the present invention concerns compounds according to formula (V), which compounds may be made using the method according to the present invention:
(Ar—SO
2
—)
m
—QH—(—SO
2
—R
1
)
n
(V)
wherein Ar is an aromatic group derived from an aromatic compound; wherein Q is C or N; wherein each R
1
is independently selected from the group consisting of aliphatic and aromatic groups, which may or may not be saturated, unsaturated, straight-chain, branched, cyclic, heteroatomic, polymeric, halogenated, fluorinated or substituted; wherein at least one R
1
contains at least one highly acidic group selected from sulfonic acid, carboxylic acid and phosphonic. acid; wherein m and N are each greater than 0; wherein m+n=2 when Q is N; and wherein m+n=3 when Q is C.
What has not been described in the art, and is provided by the present invention, is a simple method of synthesizing aromatic imides and aromatic methylidynetrissulfonyl species by direct substitution of aromatic species, including pre-existing aromatic polymers, by use of the reactants described herein.
In this application:
“highly acidic” means having a pKa<5;
“highly halogenated” means containing halogen in an amount of 40 wt % or more, but typically 50 wt % or more, and more typically 60 wt % or more; and
“highly fluorinated” means containing fluorine in an amount of 40 wt % or more, but typically 50 wt % or more, and more typically 60 wt % or more; and
“substituted” means, for a chemical species, substituted by conventional substituents which do not interfere with the desired product or process, e.g., substituents can be alkyl, alkoxy, aryl, phenyl, halo (F, Cl, Br, I) cyano, nitro, etc.
It is an advantage of the present invention to provide a simple and convenient synthetic route to aromatic-imide and aromatic-methylidynetrissulfonyl electrolytes, including solid polymer electrolytes, which are useful in electrochemical devices such as batteries and fuel cells.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention provides a method of making aromatic-imide and aromatic-methylidynetrissulfonyl species by reaction of aromatic species with a reactant according to formula (I):
(X—SO
2
—)
m
—QH—(—SO
2
—R
1
)
n
(I)
wherein Q is C or N; wherein each X is independently selected from the group consisting of halogens; wherein each R
1
is independently selected from the group consisting of wherein R
1
is selected from the group consisting of aliphatic and aromatic groups, which may or may not be saturated, unsaturated, straight-chain, branched, cyclic, heteroatomic, polymeric, halogenated, fluorinated or substituted; wherein m is greater than 0; wherein m+n=2 when Q is N; and wherein m+n=3 when Q is C.
For the reactant according to formula (I), Q may be C or N but is more typically N. Where Q is N, m may be 1 or 2. Where Q is C, m may be 1, 2 or 3, but is typically 1 or 2. Each X is a halogen, typically F or Cl, and most typically Cl.
R
1
is any suitable group that does not interfere with the synthesis according to the present invention and which provides a product having desired characteristics. Each Rmay be aromatic or aliphatic; may be saturated or unsaturated; maybe straight-chain, branched, or cyclic; may be heteroatomic or non-heteroatomic; may comprise a polymer; and may additionally be substituted including in particular halogenation, including in particular fluorination. R
1
typically comprises between 0 and 20 carbon atoms, more typically 0 to 8 carbon atoms, more typically 0 to 4 carbon atoms. Where the product species is intended for use as an electrolyte, R
1
is typically highly halogenated, more typically highly fluorinated, more typically perhalogenated, and most typically perfluorinated. Where the product species is intended for use as an electrolyte, R
1
is typically selected from: trihalomethyl, pentahaloethyl, heptahalopropyl, and nonahalobutyl, more typically where halogen substituents are selected from F and Cl. More typically, R
1
is selected from: trifluoromethyl, pentafluoroethyl, heptafluoropropyl, and nonafluorobutyl, most typically trifluoromethyl.
R
1
may advantageously contain additional highly acidic groups, typically including sulfonic acids, carboxylic acids and phosphonic acids, most typically sulfonic acid groups. R
1
may contain the highly acidic group according to formula (IV):
wherein Q and X are as defined above, wherein R
1
, is selected from the same group as R
1
defined above except that R
1
, is typically not another group according to formula (IV), wherein p+q=1 when Q is N; and wherein p+q&
3M Innovative Properties Company
Dahl Philip Y.
O'Sullivan Peter
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