U.S. patent application number 15/717038 was filed with the patent office on 2019-03-28 for oxygen permeable monomers, polymers and ionomers and methods of making the same.
The applicant listed for this patent is Nissan North America, Inc.. Invention is credited to Rameshwar Yadav.
Application Number | 20190092882 15/717038 |
Document ID | / |
Family ID | 65806478 |
Filed Date | 2019-03-28 |
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United States Patent
Application |
20190092882 |
Kind Code |
A1 |
Yadav; Rameshwar |
March 28, 2019 |
Oxygen Permeable Monomers, Polymers and Ionomers and Methods of
Making the Same
Abstract
An oxygen permeable polymer has the following formula:
##STR00001## wherein R.sub.S is a non-sulfonyl halide portion of a
sulfonyl halide monomer or polymer; X.sub.P is --NH or --NHCO; A is
an optionally substituted alkyl; L is 0, 1 or 2; m is 2 or 3; Z is
H or CH.sub.3; and n is 5-m. The polymer can be used in air
separation devices, air concentrators, and in electrodes for
electrochemical devices.
Inventors: |
Yadav; Rameshwar; (Novi,
MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Nissan North America, Inc. |
Franklin |
TN |
US |
|
|
Family ID: |
65806478 |
Appl. No.: |
15/717038 |
Filed: |
September 27, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01D 2256/12 20130101;
B01D 71/68 20130101; B01D 71/28 20130101; B01J 20/265 20130101;
H01M 8/103 20130101; C08F 8/30 20130101; B01D 71/32 20130101; B01D
53/228 20130101; C08F 2810/50 20130101; C08F 12/30 20130101; C08F
2800/10 20130101; C08F 8/28 20130101; H01M 4/8663 20130101; B01J
39/20 20130101; C08F 8/32 20130101; H01M 8/1027 20130101; C08F 8/32
20130101; C08F 214/262 20130101; C08F 8/28 20130101; C08F 8/30
20130101; C08F 212/34 20130101; C08F 8/28 20130101; C08F 8/30
20130101; C08F 212/14 20130101; C08F 8/28 20130101; C08F 8/30
20130101; C08F 212/30 20200201 |
International
Class: |
C08F 12/30 20060101
C08F012/30; C08F 8/32 20060101 C08F008/32; B01J 39/20 20060101
B01J039/20; C08F 8/28 20060101 C08F008/28; B01D 53/22 20060101
B01D053/22; B01D 71/28 20060101 B01D071/28; H01M 4/86 20060101
H01M004/86; B01D 71/32 20060101 B01D071/32 |
Claims
1. An oxygen permeable polymer having the following formula:
##STR00013## wherein R.sub.s is a non-sulfonyl halide portion of a
sulfonyl halide monomer or polymer; X.sub.P is --NH or --NHCO; A is
an optionally substituted alkyl; L is 0, 1 or 2; m is 2 or 3; Z is
H or CH.sub.3; and n is 5-m.
2. The oxygen permeable polymer of claim 1, produced from reacting
the sulfonyl halide monomer or polymer with an oxygen absorbing
compound having the following formula: ##STR00014## wherein X is
--NH.sub.2, --COOH, --COOR or --COH; and R is ether or ester.
3. The oxygen permeable polymer of claim 2, wherein the oxygen
absorbing compound is a benzoic acid-based compound and the
sulfonyl halide monomer or polymer is treated with ammonia to
convert a sulfonyl halide portion to a sulfonamide prior to
reacting with the oxygen absorbing compound.
4. The oxygen permeable polymer of claim 3, wherein the oxygen
absorbing compound is gallic acid, an ester of gallic acid, an
ether of gallic acid, 2,4,5-trihydroxybenzoic acid,
2,3,4-trihydroxybenzoic acid, or 3,4,5-trihydroxybenzoic acid.
5. The oxygen permeable polymer of claim 2, wherein the oxygen
absorbing compound comprises 5-(2-aminoethyl)-pyrogallol,
5-(aminomethyl)benzene-1,2,4-triol,
5-(aminomethyl)benzene-1,2,3-triol,
5-(2-aminoethyl)-6-methylbenzene-1,2,4-triol,
5-(2-aminoethyl)-3-methylbenzene-1,2,4-triol,
5-(2-aminoethyl)-3,6-dimethylbenzene-1,2,4-triol,
5-(2-amino-1-hydroxyethyl)-1,2,4-benzenetriol,
4-aminobenzene-1,2,3-triol, 2,3,5-trihydroxyphenethylamine,
3,4-dihydroxyphenethylamine, 3,4,5-trihydroxyphenethylamine,
2-hydroxydopamine or 5-hydroxydopamine.
6. The oxygen permeable polymer of claim 2, wherein the oxygen
absorbing compound is an aldehyde-based compound and the sulfonyl
halide monomer or polymer is treated with ammonia to convert a
sulfonyl halide portion to a sulfonamide prior to reacting with the
oxygen absorbing compound.
7. The oxygen permeable polymer of claim 6, wherein the oxygen
absorbing compound is 3,4,5-trihydroxybenzaldehyde,
2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde,
2,4,6-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde,
2,3,5-trihydroxybenzaldehyde or 2,3,4-trihydroxyacetophenone.
8. An air separation device comprising the oxygen permeable polymer
of claim 1.
9. An electrode of an electrochemical device comprising an ionomer
and the oxygen permeable polymer of claim 1.
10. A battery comprising the electrode of claim 9.
11. A fuel cell comprising the electrode of claim 9.
12. The oxygen permeable polymer of claim 1, further comprising a
proton conductor SO.sub.3H as shown in the following formula:
##STR00015##
13. A method of making an oxygen permeable polymer, comprising:
reacting under a mild base condition a sulfonyl halide monomer or
polymer (1) with an oxygen absorbing compound (2) to produce the
oxygen permeable polymer (3): ##STR00016## wherein: R.sub.s is a
non-sulfonyl halide portion of the sulfonyl halide monomer or
polymer and Y is F or Cl; X is --NH.sub.2, --COOH, --COOR, or --COH
and R is an ester or an ether; A is an optionally substituted
alkyl; L is 0, 1 or 2; m is 2 or 3; Z is H or CH3; n is 5-m; and
X.sub.P is --NH or --NHCO; and when X is --COOH, --COOR or --COH,
the reacting comprises first treating the sulfonyl halide monomer
or polymer with ammonia to convert a sulfonyl halide portion to a
sulfonamide.
14. The method of claim 13, wherein the reacting under a mild base
condition comprises: soaking the sulfonyl halide monomer or polymer
or the sulfonamide in a solvent; adding a base to form the mild
base condition; adding the oxygen absorbing compound; and reacting
at a temperature of 100.degree. C. or less for a period of
time.
15. The method of claim 14, wherein the period of time is greater
than twelve hours.
16. The method of claim 13, wherein X is --COOH or --COOR and the
oxygen absorbing compound is gallic acid, an ester of gallic acid,
an ether of gallic acid, 2,4,5-trihydroxybenzoic acid,
2,3,4-trihydroxybenzoic acid, or 3,4,5-trihydroxybenzoic acid.
17. The method of claim 13, wherein X is --COH and the oxygen
absorbing compound is 3,4,5-trihydroxybenzaldehyde,
2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde,
2,4,6-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde,
2,3,5-trihydroxybenzaldehyde or 2,3,4-trihydroxyacetophenone.
18. The method of claim 13, wherein X is --NH.sub.2 and the oxygen
absorbing compound comprises 5-(2-aminoethyl)-pyrogallol,
5-(aminomethyl)benzene-1,2,4-triol, 5-(aminomethyl)b
enzene-1,2,3-triol, 5-(2-aminoethyl)-6-methylbenzene-1,2,4-triol,
5-(2-aminoethyl)-3-methylbenzene-1,2,4-triol,
5-(2-aminoethyl)-3,6-dimethylbenzene-1,2,4-triol,
5-(2-amino-1-hydroxyethyl)-1,2,4-benzenetriol,
4-aminobenzene-1,2,3-triol, 2,3,5-trihydroxyphenethylamine,
3,4-dihydroxyphenethylamine, 3,4-trihydroxyphenethylamine,
2-hydroxydopamine or 5-hydroxydopamine.
19. A method of making an oxygen-conducting and proton-conducting
ionomer, comprising the method of claim 13, and further comprising:
adding a proton conducting functional group to an unreacted portion
of the sulfonyl halide monomer or polymer, wherein the
oxygen-conducting and proton-conducting ionomer has the following
formula: ##STR00017##
20. The method of claim 19, wherein adding the proton conducting
functional group comprises: hydrolyzing the unreacted portion of
the sulfonyl halide monomer or polymer with a base and an alcohol;
ion exchanging the hydrolyzed unreacted portion of the sulfonyl
halide monomer or polymer with an acid to form an oxygen permeable
and proton conducting material.
Description
TECHNICAL FIELD
[0001] This disclosure relates to improved oxygen permeable
monomers, polymers and ionomers and methods of making the same.
BACKGROUND
[0002] Oxygen is used in many electrochemical devices such as fuel
cells and lithium air batteries. Oxygen is also used in fuel
combustion systems that have innumerable applications including
internal combustion engines, space crafts, and submerged vehicles.
Air, which is typically used as the oxygen source, has only 21%
oxygen, which limits the performance of these devices. Increasing
the oxygen molar concentration above 21% would enhance the power
density and efficiency of these devices. Air separation
technologies exist, but have limited selectivity of oxygen and are
non-ionic and do not provide improved conduction of ions.
[0003] Conventional ionomers used in electrocatalyst in
electrochemical devices conduct protons well, but poorly transport
oxygen. Improved oxygen transport through electrodes of
electrochemical devices would improve performance.
SUMMARY
[0004] Disclosed herein are oxygen permeable monomers, polymers,
co-polymers and ionomers for use in electrochemical devices such as
fuel cells and batteries, and also for use in air separation
devices or oxygen concentrators. Methods of making the oxygen
permeable monomers, polymers, co-polymers and ionomers are also
disclosed.
[0005] An embodiment of an oxygen permeable polymer disclosed
herein has the following formula:
##STR00002##
wherein R.sub.s is a non-sulfonyl halide portion of a sulfonyl
halide monomer or polymer; X.sub.P is --NH or --NHCO; A is an
optionally substituted alkyl; L is 0, 1 or 2; m is 2 or 3; Z is H
or CH.sub.3; and n is 5-m.
[0006] An embodiment of an oxygen-conducting and a
proton-conducting ionomer disclosed herein has the following
formula:
##STR00003##
wherein R.sub.s is a non-sulfonyl halide portion of a sulfonyl
halide monomer or polymer; X.sub.P is --NH or --NHCO; A is an
optionally substituted alkyl; L is 0, 1 or 2; m is 2 or 3; Z is H
or CH.sub.3; and n is 5-m
[0007] A method of making an oxygen permeable monomer or polymer as
disclosed herein comprises reacting under a mild base condition a
sulfonyl halide monomer or polymer (1) with an oxygen absorbing
compound (2) to produce the oxygen permeable polymer (3):
##STR00004##
wherein R.sub.S is a non-sulfonyl halide portion of the sulfonyl
halide monomer or polymer and Y is F or Cl; X is --NH.sub.2,
--COOH, --COOR, or --COH and R is an ester or an ether; A is an
optionally substituted alkyl; L is 0, 1 or 2; m is 2 or 3; Z is H
or CH.sub.3; n is 5-m; and X.sub.P is --NH or --NHCO. When X is
--COOH, --COOR or --COH, the reacting comprises first treating the
sulfonyl halide monomer or polymer with ammonia to convert a
sulfonyl halide portion to a sulfonamide.
DETAILED DESCRIPTION
[0008] In electrochemical devices, the concentration of oxygen and
the transport of oxygen molecules to reaction sites directly
determine the power density output of these devices. In these
devices, oxidized ions such as H.sup.+ and Li.sup.+ ions migrate
from anode to cathode to react with oxygen to complete the
electrochemical reaction.
[0009] Besides the natural fixed oxygen concentration when using
air, oxygen is also limited by transport resistance due to dense
and non-permeable polymeric ionomers and binders in active cathode
materials. The cathode structure is intricate and uses dense
polymeric ionomers and polymeric binders to hold together loose
electrocatalyst particles. The polymeric ionomer also need to
conduct ions such as H.sup.+ and Li.sup.+ to the reaction sites.
Conventional ionomers such as those manufactured as Nation.RTM. and
Aquivion.RTM., or manufactured by 3M, have limited oxygen
permeability and also inhibit the oxygen transport to the reaction
sites. These fluorinated compounds, which form conventional
ionomers, play the dual roles of electrolyte/membrane in which
there should be no oxygen transport, and binder in the electrode
which should facilitate oxygen transport. Conventional ionomer
material is unable to meet the demand of both electrolyte/membrane
and binder.
[0010] The materials disclosed herein have high oxygen transport
properties due to covalent linking of various oxygen-absorbing
functional groups. This new class of material, which can be a
monomer, polymer, or co-polymer or further formulated into an
ionomer, addresses the need for a highly oxygen permeable material
that can be used in electrochemical devices. The materials
disclosed herein can be used to promote oxygen transport in fuel
cells devices such as PEMFC, AFC, SOFC, MCFC, and electrochemical
cells such as metal-air, Li-air, Mg-air, Zn-air, Al-air, K-air,
Na-Air, Fe-air, Si-air.
[0011] The materials disclosed herein also address the challenges
of air separation technologies in which current air separation
materials have very limited oxygen permeability. This leads to low
air separation efficiency. The oxygen permeable monomers, polymers
or co-polymers disclosed herein can be used as air-separation
membranes, air-separation filters, air-separation particles, etc.
in applications such as fuel combustion and oxygen enhanced
combustion devices in spacecraft, rocket, and submerged vehicles,
as non-limiting examples, medical devices and therapies, oxygen
therapy, chemical production such as hydrogen peroxide, ethylene
oxide, sulfuric acid and nitric acid, steel industry processes,
cutting processes, oxy-acetylene welding, melting of metals,
wastewater and effluent treatment processes.
[0012] An oxygen permeable polymer disclosed herein has the
following formula:
##STR00005##
wherein R.sub.s is a non-sulfonyl halide portion of a sulfonyl
halide monomer or polymer; X.sub.P is --NH or --NHCO; A is an
optionally substituted alkyl; L is 0, 1 or 2; m is 2 or 3; Z is H
or CH.sub.3; and n is 5-m.
[0013] As used herein, "oxygen permeable" means oxygen can diffuse
through the polymer. This property provides a polymer that can be
used to transport oxygen through electrodes by allowing the oxygen
to diffuse through the material rather than obstruct the material.
This property provides a polymer that can preferentially diffuse
oxygen over nitrogen, thereby concentrating the oxygen that
diffuses through the material, and separating the oxygen from the
nitrogen.
[0014] As used herein, the term "polymer" includes co-polymers.
When R.sub.s is a non-sulfonyl halide portion of a sulfonyl halide
monomer, the resulting oxygen permeable monomer is polymerized by
processes known to those skilled in the art to form the oxygen
permeable polymer. Polymerization can occur prior to reacting the
precursor. The polymer precursor can be reacted to form the oxygen
permeable monomer and then polymerized. As non-limiting examples, a
polymer precursor can be a polymer or co-polymer that does not need
to be polymerized. The polymer precursor can be a polymer or
co-polymer that requires additional polymerization.
[0015] To produce the oxygen permeable polymer, a sulfonyl halide
monomer or polymer (1) is reacted under mild base conditions with
an oxygen absorbing compound (2) to produce the oxygen permeable
polymer (3), as shown in the reaction below:
##STR00006##
[0016] In the sulfonyl halide monomer or polymer (1), R.sub.s is
the non-sulfonyl halide portion of the sulfonyl halide monomer or
polymer and Y is F or Cl.
[0017] In the oxygen absorbing compound (2), X is --NH.sub.2,
--COOH, --COOR, or --COH and R is an ester or an ether; A is an
optionally substituted alkyl; L is 0, 1 or 2; m is 2 or 3; Z is H
or CH.sub.3; and n is 5-m.
[0018] When X is --COOH, --COOR or --COH in the oxygen absorbing
compound, the sulfonyl halide monomer or polymer is first treated
with ammonia to convert the sulfonyl halide portion to a
sulfonamide, as shown below. When X is --NH.sub.2 in the oxygen
absorbing compound, there is no need to convert the sulfonyl halide
portion of the monomer or polymer.
##STR00007##
[0019] The sulfonyl halide monomer or polymer can be any
hydrocarbon, partial hydrocarbon, perfluorocarbon, fluorinated,
partially fluorinated polymer, co-polymer or monomer. Non-limiting
examples include: Nafion.TM. polymer or resins in SO.sub.2F form;
Aquivion.TM. polymer or resins in SO.sub.2F form; polymer,
co-polymer or monomer of 2-allyloxy-1,1,2,2-tetrafluoro ethane
sulfonyl fluoride; polymer, co-polymer or monomer of
4-(trifluorovinyl) benzene sulfonyl fluoride; polymer, co-polymer
or monomer of p-styrene sulfonyl fluoride/chloride; polymer,
co-polymer or monomer of perfluoro (3-oxapent-4-ene) sulfonyl
fluoride; polymer, co-polymer or monomer of ethene sulfonyl
fluoride; polymer, co-polymer or monomer of 2-propene-1-sulfonyl
chloride; and polymer, co-polymer or monomer of perfluoro
(4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride, polymer,
co-polymer or monomer of
1,1,2,2-tetrafluoro-2-[(1,1,2,2-tetrafluoro-3-butenyl)oxy]-ethane
sulfonyl fluoride. Other sulfonyl halide monomers and polymers that
can be used herein are disclosed in U.S. Pat. No. 9,403,746; U.S.
Pat. No. 9,350,035; U.S. Pat. No. 9,212,246; and U.S. Pat. No.
9,694,357.
[0020] Formulas of sulfonyl halide monomers or polymers that will
produce the oxygen permeable polymer (3) are shown as non-limiting
examples below:
##STR00008##
[0021] The oxygen absorbing compound can be a benzoic acid-based
compound, where X is --COOH or --COOR, and R is an ether or an
ester. Non-limiting examples of a benzoic acid-based oxygen
absorbing compound include gallic acid, an ester of gallic acid, an
ether of gallic acid, 2,4,5-trihydroxybenzoic acid,
2,3,4-trihydroxybenzoic acid, and 3,4,5-trihydroxybenzoic acid.
[0022] The oxygen absorbing compound can be an aldehyde-based
compound, where X is --COH. Non-limiting examples of an
aldehyde-based oxygen absorbing compound include
3,4,5-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde,
2,3,4-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde,
2,3,6-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde and
2,3,4-trihydroxyacetophenone.
[0023] When the oxygen absorbing compound is a benzoic acid-based
compound or an aldehyde-based compound, the sulfonyl halide monomer
or polymer is treated with ammonia to convert a sulfonyl halide
portion to a sulfonamide prior to reacting the sulfonyl halide
monomer or polymer with the benzoic acid-based compound or the
aldehyde-based compound.
[0024] The oxygen absorbing compound can be an amine-based
compound, where X is --NH.sub.2. Non-limiting examples of an
amine-based oxygen absorbing compound include
5-(2-aminoethyl)-pyrogallol, 5-(aminomethyl)benzene-1,2,4-triol,
5-(aminomethyl)benzene-1,2,3-triol,
5-(2-aminoethyl)-6-methylbenzene-1,2,4-triol,
5-(2-aminoethyl)-3-methylbenzene-1,2,4-triol,
5-(2-aminoethyl)-3,6-dimethylbenzene-1,2,4-triol,
5-(2-amino-1-hydroxyethyl)-1,2,4-benzenetriol,
4-aminobenzene-1,2,3-triol, 2,3,5-trihydroxyphenethylamine,
3,4-dihydroxyphenethylamine, 3,4,5-trihydroxyphenethylamine,
2-hydroxydopamine and 5-hydroxydopamine.
[0025] When an amine-based oxygen absorbing compound is used, there
is no need to convert the sulfonyl halide portion of the monomer or
polymer to a sulfonamide as the amine constituent is already
present.
[0026] Other oxygen absorbing compounds are contemplated herein.
Non-limiting examples include 2-pyridylamidoxime,
3-pyridylamidoxime, 4-pyridylamidoxime, 4-methylbenzamide oxime,
PFPE (perfluoro polyether) amine, diamine or any other PFPE based
amines, hydrocarbon, fluorinated or fluorine treated polyethylene
glycol (PEG) and polyethylene oxide (PEO) based compound, any
single-arm or multi-arm primary amine or carboxylic acid, and
hydrocarbon and fluorinated or fluorine treated of the following:
poly(ethylene glycol) bis(amine), amino-(PEG).sub.n-OH,
hydroxyl-(PEG).sub.n-amine (HO-(PEG).sub.n-NH.sub.2), Y shape
(PEG).sub.n amine (Y-(PEG).sub.n-NH.sub.2),
O-(2-aminoethyl)polyethylene glycol (PEG)n, fluorinated
poly(ethylene glycol)2-aminoethyl ether acetic acid,
4arm-(PEG)n-amine, 2arm-(PEG)n-amine, 3arm-(PEG)n-amine,
larm-(PEG)n-amine or multi-arm (PEG)n-amine, methoxy (PEG)n-amine,
4arm-(PEG)n-glutaric acid, multi arm-PEG)n-glutaric acid, multi
arm-PEG)n-COOH acid PEG carboxylic acid, PEO carboxylic acid, and
NH.sub.2-(PEG).sub.n-COOH, where n is obtained by molecular
weight.
[0027] To react the sulfonyl halide or sulfonamide of the monomer
or polymer with the oxygen absorbing compound, the monomer or
polymer is soaked in a solvent such as acetonitrile, water or any
other organic solvent. A mild base condition is formed by adding an
organic or inorganic base such as pyridine, K.sub.2CO.sub.3, KOH or
NaOH. The oxygen absorbing compound is added to the mixture and
reacted below 100.degree. C. for at least twelve hours to achieve
satisfactory conversion to the oxygen permeable polymer. In
particular, the reaction can be performed at a temperature between
about 90.degree. C. and 100.degree. C. The oxygen permeable polymer
can be retrieved from the reaction vessel, rinsed with deionized
water several times and then boiled in deionized water to remove
any trace of residuals from the reaction.
[0028] One example of an oxygen permeable polymer and method of
making is shown below, using 5-(2-aminoethyl)-pyrogallol as the
oxygen absorbing compound and Nafion.TM. polymer in sulfonyl
fluoride form as the sulfonyl halide monomer or polymer.
##STR00009##
[0029] Another example of an oxygen permeable polymer and method of
making is shown below, using 4-(trifluoro vinyl) benzene sulfonyl
fluoride monomer as the sulfonyl halide monomer or polymer and
gallic acid as the oxygen absorbing compound. Because gallic acid
is a benzoic acid-based oxygen absorbing compound, the 4-(trifluoro
vinyl) benzene sulfonyl fluoride monomer is first converted with
ammonia to 4-(trifluoro vinyl) benzene sulfonamide monomer.
##STR00010##
[0030] Another example of an oxygen permeable polymer and method of
making is shown below, using a crosslinked polymer in sulfonyl
fluoride form as the sulfonyl halide monomer or polymer and
3,4,5-trihydroxybenzaldehyde as the oxygen absorbing compound.
Because 3,4,5-trihydroxybenzaldehyde is an aldehyde-based oxygen
absorbing compound, the crosslinked polymer in sulfonyl fluoride
form is first converted with ammonia to a crosslinked polymer in
sulfonamide form, not shown.
##STR00011##
[0031] The oxygen permeable polymers disclosed herein can be used
as material for air-separation devices or oxygen concentration
devices for any device or process in which oxygen is used. The
oxygen permeable polymers can be formed into a membrane filter
through which air flows, as an example. The oxygen permeable
polymers can be used in a form such as a pellet that can be used in
an absorption column, for example.
[0032] The oxygen permeable polymers disclosed herein can also be
used in electrodes of electrochemical devices. The oxygen permeable
polymers can be mixed into the active material along with an
ionomer to provide both oxygen transport and proton transport
through the electrode. Alternatively, the oxygen permeable polymers
disclosed herein can be further formed into an oxygen-conducting
and proton-conducting ionomer for use in electrochemical cell
electrodes.
[0033] The reaction producing the oxygen permeable polymer will
convert some portion of the sulfonyl halide or sulfonamide sites to
an oxygen permeable site, depending on the conditions in which the
reaction takes place. Reaction conditions, such as length of time
and temperature of the reaction, can be adjusted to convert any
portion of the sulfonyl halide or sulfonamide sites to oxygen
permeable sites as desired. The remaining sulfonyl halide or
sulfonamide sites not converted to an oxygen permeable site can be
converted to a proton conducting function group such as sulfonic
acid. Accordingly, an oxygen-conducting and proton-conducting
ionomer is produced.
[0034] The method of making an oxygen-conducting and
proton-conducting ionomer from the oxygen permeable polymers
disclosed herein comprises adding a proton conducting functional
group to an unreacted portion of the sulfonyl halide monomer or
polymer. The oxygen-conducting and proton-conducting ionomer has
the following formula:
##STR00012##
wherein R.sub.s is a non-sulfonyl halide portion of a sulfonyl
halide monomer or polymer; X.sub.P is --NH or --NHCO; A is an
optionally substituted alkyl; L is 0, 1 or 2; m is 2 or 3; Z is H
or CH.sub.3; and n is 5-m.
[0035] The proton conducting functional groups can be added by
hydrolyzing the unreacted portion of the sulfonyl halide monomer or
polymer with a base and an alcohol and ion exchanging the
hydrolyzed unreacted portion of the sulfonyl halide monomer or
polymer with an acid to form the oxygen permeable and proton
conducting material.
[0036] The base can be, for example, KOH or NaOH and the alcohol
can be, for example, methanol, dimethyl sulfoxide, or other ethers.
For example, 15 wt. % base and 35 wt. % alcohol can be used with
water being the remaining 50 wt. %. The ion exchange is with
mineral acids, including, for example, HNO.sub.3 or
H.sub.2SO.sub.4.
[0037] While the disclosure has been described in connection with
certain embodiments, it is to be understood that the disclosure is
not to be limited to the disclosed embodiments but, on the
contrary, is intended to cover various modifications and equivalent
arrangements included within the scope of the appended claims,
which scope is to be accorded the broadest interpretation so as to
encompass all such modifications and equivalent structures as is
permitted under the law.
* * * * *