Polyvinylidene fluoride ionomers containing pendant...

Details Polyvinylidene fluoride ionomers containing pendant... Polyvinylidene fluoride ionomers containing pendant...

2001-05-10

2003-12-23

Wilson, Donald R. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S241000, C526S243000, C525S326200, C525S362000, C525S366000, C525S367000, C525S368000, C525S369000, C524S544000, C524S379000, C524S280000

Reexamination Certificate

active

06667377

ABSTRACT:

FIELD OF THE INVENTION
This invention deals with substantially fluorinated but not perfluorinated ionomers, and related ionic and nonionic monomers, having pendant groups containing fluorosulfonyl methide or fluorosulfonyl imide derivatives and univalent metal salts thereof, and with the uses of said ionomers in electrochemical applications such as batteries, fuel cells, electrolysis cells, ion exchange membranes, sensors, electrochromic windows, electrochemical capacitors, and modified electrodes. Certain compositions of the invention are also useful as strong acid catalysts.
BACKGROUND OF THE INVENTION
Copolymers of vinylidene fluoride (VF2) with vinyl alkoxy sulfonyl halides are known in the art.
The disclosures in Ezzell et al. (U.S. Pat. No. 4,940,525) encompass copolymers of VF2 with vinyl ethoxy sulfonyl fluorides containing one ether linkage. Disclosed is a process for emulsion polymerization of tetrafluoroethylene (TFE) with the vinyl ethoxy comonomer.
Connolly et al. (U.S. Pat. No. 3,282,875) disclose the terpolymer of VF2 with perfluorosulfonyl fluoride ethoxy propyl vinyl ether (PSEPVE) and hexafluoropropylene (HFP). They broadly teach an emulsion polymerization process said to be applicable to copolymerization of vinyl ethers with any ethylenically unsaturated comonomer, with greatest applicability to fluorinated monomers.
DesMarteau (U.S. Pat. No. 5,463,005), incorporated herein by reference, discloses substituted perfluoro-olefins of the formula
where X═C 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=perfluoroalkyl or F, and m=0 or 1. Further disclosed by DesMarteau are copolymers formed by aqueous emulsion polymerization of the sodium salt form of (I) with tetrafluoroethylene. Further disclosed are compositions consisting of the acid-form of the imide copolymer of DesMarteau in combination with dimethylformamide (hereinafter DMF) to provide a conductive composition. Membranes or films of the acid imide polymer are cast from solution. Copolymers of the substituted perfluoroolefins with VF2 are not disclosed in U.S. Pat. No. 5,463,005.
Armand (U.S. Pat. No. 4,818,644) discloses metal salts based on anions having the structure R
f
—SO
2
CR—SO
2
R′
f
where R
f
and R′
f
are perfluorinated groups having from 1 to 10 carbon atoms and R is a hydrogen or an alkyl group having from 1 to 30 carbon atoms. The lithium salts of these compounds are useful in combination with organic solvents or macromolecular solvents for making electrolyte solutions for lithium batteries. Armand et al. further disclose (EP 0 850 921) salts and ionomeric polymers derived from malononitrile Z—C(CN)2 where Z represents an electron-withdrawing group and Z can also contain a polymerizable function. Ionomers based on these compounds are disclosed having styrenic or vinyl functional groups for polymerization. Copolymers of these monomers with substantially fluorinated monomers such as VF2 are not disclosed.
Xue, Ph.D. thesis, Clemson University, 1996, discloses reactions of the type RSO
2
NHX with R′SO
2
Y with X═H, Na and Y═Cl, F to form RSO
2
N(M)SO
2
R′, where R and R′ are perfluorinated groups, in the presence of MF with M═Cs, K or in the presence of Na
2
CO
3
if X═Na and Y═Cl to form monomers represented by the formula
CF
2
═CF—OCF
2
CF(CF
3
)OCF
2
CF
2
SO
2
NMSO
2
R
f
and copolymers thereof with tetrafluoroethylene.
Armand et al, EP0850921A1 and EP0850920A1, provide a tremendous list of imide- and methide-containing ionic species, including polymers incorporating them. However, no means for making these compositions is provided, and no distinction is made among the compounds from the standpoint of utility. No disclosure is made of the particular utility and surprising attributes of the compositions of the present invention.
SUMMARY OF THE INVENTION
The present invention provides for an ionic polymer (ionomer) comprising monomer units of VF2 and further comprising 0.5-50 mol-% of monomer units having pendant groups comprising the radical represented by the formula
—(OCF
2
CFR)
a
OCF
2
(CFR′)
b
SO
2
X
−
(M
+
)(Y)(Z)
c
  (I)
wherein
R and R′ are independently selected from F, Cl or a perfluoroalkyl group having 1 to 10 carbon atoms optionally substituted by one or more ether oxygens;
a=0, 1 or 2;
b=0 to 6;
M
+
is H
+
or a univalent metal cation;
X is C or N with the proviso that c=1 when X is C and c=0 when X is N; when c=1, Y and Z are electron-withdrawing groups selected from the group consisting of CN, SO
2
R
f
, SO
2
R
3
, P(O)(OR
3
)
2
, CO
2
R
3
, P(O)R
3
2
, C(O)R
f
C(O)R
3
, and cycloalkenyl groups formed therewith
wherein R
f
is a perfluoroalkyl group of 1-10 carbons optionally substituted with one or more ether oxygens;
R
3
is an alkyl group of 1-6 carbons optionally substituted with one or more ether oxygens, or an aryl group optionally further substituted;
Y and Z are the same or different;
or, when c=0, Y may be an electron-withdrawing group represented by the formula —SO
2
R
f
′ where R
f
′ is the radical represented by the formula —(R
f
″SO
2
N
−
(M
+
)SO
2
)
m
R
f
′″ where m=0 or 1, and R
f
″ is —C
n
F
2n
— and R
f
′″ is —C
n
F
2n+1
where n=1-10, optionally substituted with one or more ether oxygens.
The present invention further provides for an ethylenically unsaturated composition represented by the formula
CF
2
═CF(OCF
2
CFR)
a
OCF
2
(CFR′)
b
SO
2
C
−
(M
+
)(Y)(Z)  (II)
wherein
R and R′ are independently selected from F, Cl or a perfluoroalkyl group having 1 to 10 carbon atoms optionally substituted with one or more ether oxygens;
a=0, 1 or 2;
b=0 to 6;
M
+
is H
+
or a univalent metal cation;
Y and Z are electron-withdrawing groups selected from the group consisting of CN, SO
2
R
3
, P(O)(OR
3
)
2
, CO
2
R
3
, P(O)R
3
2
, C(O)R
f
C(O)R
3
, and cycloalkenyl groups formed therewith wherein R
f
is a perfluoroalkyl group of 1-10 carbons optionally substituted with one or more ether oxygens;
R
3
is an alkyl group of 1-6 carbons optionally substituted with one or more ether oxygens, or an aryl group optionally further substituted;
Y and Z are the same or different.
The present invention further provides a method for making a methide ionomer the method comprising, combining in an inert organic liquid at a temperature in the range of 0-150° C. a copolymer comprising monomer units of VF2 and 0.5-50 mol-% of monomer units represented by the formula:
CF
2
═CF(OCF
2
CFR)
a
OCF
2
(CFR′)
b
SO
2
F  (III)
wherein R and R′ are independently selected from F, Cl or a perfluoroalkyl group having 1 to 10 carbon atoms optionally substituted with one or more ether oxygens, a=0, 1 or 2, and b=0 to 6; with a carbanion derived from a methylene compound represented by the formula CH
2
YZ wherein Y and Z are electron-withdrawing groups selected from the group consisting of CN, SO
2
R
f
, SO
2
R
3
, P(O)(OR
3
)
2
, CO
2
R
3
, P(O)R
3
2
, C(O)R
f
C(O)R
3
, and cycloalkenyl groups formed therewith, wherein R
f
is a perfluoroalkyl group of 1-10 carbons, optionally substituted with one or more ether oxygens, R
3
is an alkyl group of 1-6 carbons, optionally substituted with one or more ether oxygens or an aryl group optionally further substituted; and wherein Y and Z may be either the same or different to form a reaction mixture; reacting said reaction mixture until the desired degree of conversion has been achieved; and, removing the majority of said organic liquid.
The present invention further provides a method for making a methide composition the method comprising, combining an inert organic solvent at a temperature in the range of 0-100° C. a composition represented by the formula
CF
2
A—CFA(OCF
2
CFR)
a
OCF
2
(CFR&pr

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