CA2228466A1 - New improved ion exchange membranes, their methods of preparation and their uses - Google Patents
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Abstract
Di-functional monomers of general formula [T~SO2~Y~SO2T']-M+
where:
- T or T' are identical or different and each represent an organic radical having at least one polymerization-active function;
- M+ represents a cation, inorganic or organic, preferably chosen among: H+, Li+, Na+, K+, 1/2Mg2+, 1/2Ca2+, 1/2Ba2+, 1/2Zn2+ and other transition metals, 1/3La3+
and other rare earths, ammonium, amidinium, pyridinium, imidazolium, guanidinium, sulfonium, phosphonium, iodonium, organometallic cations, all possibly including coordination ligands....
- Y represents N (nitrogen), CH, or CQ.
- Q represents an alkyl or alkylene with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents, or T or an alkyl- or an alkylene- sulfonyl group, with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents.
where:
- T or T' are identical or different and each represent an organic radical having at least one polymerization-active function;
- M+ represents a cation, inorganic or organic, preferably chosen among: H+, Li+, Na+, K+, 1/2Mg2+, 1/2Ca2+, 1/2Ba2+, 1/2Zn2+ and other transition metals, 1/3La3+
and other rare earths, ammonium, amidinium, pyridinium, imidazolium, guanidinium, sulfonium, phosphonium, iodonium, organometallic cations, all possibly including coordination ligands....
- Y represents N (nitrogen), CH, or CQ.
- Q represents an alkyl or alkylene with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents, or T or an alkyl- or an alkylene- sulfonyl group, with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents.
Description
New improved Ion Exchange Membranes, their Methods of Preparation and their Uses This invention relates to ion exchange membranes, their methods of preparation and their uses.
Previous Art:
Owing to their chemical inertness, fluorinated or perfluorinated ion exchange membranes have been selected for the chlor-alkali process and for fuel cells consuming either hydrogen or methanol. The materials presently available under the commercial names Nafion~, Flemion~, Down or materials developed by Ballard Inc. (W097/25369) are copolymers of tetrafluoroethylene; (TFE) and of perfluorovinylethers or trifluorovinylstryrene. The active monomers bear chemical functionalities which are the precursors of ionic groups of the sulfonate or carbo)rylate type. These precursors are F2C=CF-O CFZ-CF-O CFZ-CFZ-S02F
X n or:
or FZC=CF- O CFZ-GF-O (C F2-jp COZR
IX n F2C=CF ~~SOZF
where ~:
-~ X represents F~, Cl or CF3 -~ OLnL 10 -~p=lor2 -~ R = alkyl, (ethyl or methyl).
Once obtained the copolymer containing the precursors is processed into sheets then transformed into ionic form by hydrolysis (-S02F - -S03-M+; -C02R - -C02-M+}.
where:
- M:+ represents a cation, for example: H+, Li+, Na+, K+, 1/2Mg2+, 1/2Ca2+, 1/ZBa2+ and other alkaline earth metals ions, 1/2Zn2+, l/2Cu2+ and other transition metals ions, 1/3A13+~ 1/3F~e3+, 1/3Sc3+,113Y3+, lJ3La3+ and other rare earth metals ions, or an organic cation of the opium type, oxoniun, ammonium or pyridinium, guanidinium, amidinium, sulfonium, phosphonium, non substituted, partially or totally substituted by organic radicals, organometallic cations, like metalloceniums, arene-ferrocenium, alkylsilyl, alkylgermanyl, alkyltin...
Such materials hare however several important drawbacks which are summarized below:
1) the copolymers in their ionic form are untractable, yet are not dimensionally stable and swell appreciably in water and polar solvents. Only when heated at high temperature in supercritical water-lower alcools mixtures they can form inverse micelles which, upon evaporation, le<ive the materials as films. However this recast material is in a form lacking mechanical cohesiveness;
Previous Art:
Owing to their chemical inertness, fluorinated or perfluorinated ion exchange membranes have been selected for the chlor-alkali process and for fuel cells consuming either hydrogen or methanol. The materials presently available under the commercial names Nafion~, Flemion~, Down or materials developed by Ballard Inc. (W097/25369) are copolymers of tetrafluoroethylene; (TFE) and of perfluorovinylethers or trifluorovinylstryrene. The active monomers bear chemical functionalities which are the precursors of ionic groups of the sulfonate or carbo)rylate type. These precursors are F2C=CF-O CFZ-CF-O CFZ-CFZ-S02F
X n or:
or FZC=CF- O CFZ-GF-O (C F2-jp COZR
IX n F2C=CF ~~SOZF
where ~:
-~ X represents F~, Cl or CF3 -~ OLnL 10 -~p=lor2 -~ R = alkyl, (ethyl or methyl).
Once obtained the copolymer containing the precursors is processed into sheets then transformed into ionic form by hydrolysis (-S02F - -S03-M+; -C02R - -C02-M+}.
where:
- M:+ represents a cation, for example: H+, Li+, Na+, K+, 1/2Mg2+, 1/2Ca2+, 1/ZBa2+ and other alkaline earth metals ions, 1/2Zn2+, l/2Cu2+ and other transition metals ions, 1/3A13+~ 1/3F~e3+, 1/3Sc3+,113Y3+, lJ3La3+ and other rare earth metals ions, or an organic cation of the opium type, oxoniun, ammonium or pyridinium, guanidinium, amidinium, sulfonium, phosphonium, non substituted, partially or totally substituted by organic radicals, organometallic cations, like metalloceniums, arene-ferrocenium, alkylsilyl, alkylgermanyl, alkyltin...
Such materials hare however several important drawbacks which are summarized below:
1) the copolymers in their ionic form are untractable, yet are not dimensionally stable and swell appreciably in water and polar solvents. Only when heated at high temperature in supercritical water-lower alcools mixtures they can form inverse micelles which, upon evaporation, le<ive the materials as films. However this recast material is in a form lacking mechanical cohesiveness;
2) handling of TFE is hazardous, as its polymerization is corned out under pressure and my lead to runaway reactions, especially in the presence of oxygen; due to the difference in boiling points of the two monomers, it is difficult to obtain a statistical polymer corresponding to the monomer feed ratio;
3) the ionic groups tend to impart solubility to the polymer. To avoid this, the concentration of ionic groups is kept low by incorporating a large weight or mole fraction of TFE monomer and / or increasing the side chains length (n > 1), resulting in typically less than 1 milli-equivalent / graJm of ion exchangeable groups. Consequently, the conductivity is relatively low and very sensitive to the water content of the membrane, especially when in the acidic form for fuel-cell applications;
4) the permeation of methanol and of oxygen through the membrane is high, as the perfluorocarbon. part of the polymer allows easy diffusion of molecular species, resulting in cross over chemical reaction and a loss of faradaic efficiency, in particular for direct methanol fuel cE:lls (DMFC's).
Description of Invention:
Departing from prior art, we describe here the use of perfluoro-bis(vinylethers) having the highly dissociated imide, bis(sulfonylinethane) or tris(sulfonylmethane)ionic groups, as a base for crosslinked ion-exchange membranes directly obtained in their final shape (usually filins, or hollow tubes and referred thereafter as membranes) and having a high density of ionic functions. The polymerization can be carried out in concentrated solution of the monomer in its salt form. The materials thus obtained do not have the disadvantages of the previously known perfluorinated ionomers, i.e. they are dimensionally stable in the presence of all solvents, including water, yc;t are highly conductive due to the high concentration of ionic groups; the crosslinks form an excellent barner to both oxygen and methanol or other organic fuels. No ThE is necessary in the polymerization process, thereby reducing hazards. The materials can be processed into extremely thin membranes and are thus cost efficient in terms of the utilization of the monomers. Furthermore, it is easy to include the electrode materials at one or both sides of the membrane ~3uring its fabrication, either at the stage of monomer polymerization or to coat them from a slurry of the active materials in a solution of the monomer in an appropriate solvent applied to an already formed membrane and subsequent polymerization.
Besides, the strong electron withdrawing nature of the imide, polysulfonyl substituted carbanions as well as the perfluorosulfonate anion enhances the catalytic activity of the cations M+ which are specific for many important reactions. The materials are thus useful as supported catalysts when in the form exchanged with an active M+ cation. In the form of a crosslinlced material, the catalyst is easily separated mechanically from the reaction medium. Non-limiting examples of reactiions which can be catalyzed include Diels & Alder additions, Friedel & Craft reactions, aldol condensations, cationic polymerization, esterifications, acetal formation.
The bifunctional monomers of the present invention have the general formula:
~ T-S02-Y-S02T~ ~_ M+
where T or T', identical or different represent a polymerization-active radical. As examples, the T moieties is advantageously chosen among the following radicals:
F2C= Cf=- O CF2 ~F- CF Z- CFZ
X n or:
F~ F
O O
CFZ-CF-O CFZ-CFZ-X n or:
CZZ=CZ- E
denoted as:
CZ2=CZ- E
CZZ=CZ- E
E- CZ=CZZ
where:
- X represents F, Cl or CF3 - n is an integer comprised between 0 (zero) (included) and 10 - IT represents N (nitrogen), CH, CQ
- Q represents an alkyl or alkylene with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents, or T or an alkyl or alkylene sulfonyl group, with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents - E represents an ether -O-, sulfide -S-, sulfone -S02- or nothing (direct =C(Z)-aryl link).
- Z is either F ~or H.
The monomers according to the invention can be obtained by different processes. In a simple embodiment, the irnide type monomers are obtained by the following reactions:
2TS02-L + [A2N]-M+ -~ 2LA + (TS02)2N-M+
or TS02-L + [T'AN]-M+ --~ LA + [(TS02)N(S02T')]'M+
T and T', identical or different corresponding to the above definition.
Sinularly, the carb~~n-based compounds results from similar reactions:
2TS02-L + [A2CQ]-M+ ~ 2LA + [(TS02)2CQ-]M+
or:
2TS02-L + [A2CQ]-M+ -~ 2LA + [(TS02)2CQ-]M+
- L being a learning group, like an halogen, F, Cl, Br, a pseudo halogen like SCN, or an electrophilic heteroatom moieties, like N-imidazolyl, N-triazolyl, or RS02-O-, R
represents an alkyl or alkylene with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents, or T.
A represents. an M+ cation ( 1/mMm+) cation, including trialkylsilyl group, trialkylstannyl groups or tertioallryl as a proton equivalent, in which the alkyl substituents comprise from 1 to 6 carbon atoms. As example, the reaction of lithium nitride on a sufonyl fluoride may be mentioned:
2TS02F ~- Li3N --~ 2LiF + [(TS02)2N]-Li+
A is advantageously a tertioalkyl radical as this group is a precursor to a proton with the driving force being the formation of an alkene; as for instance in the case of the tertiobutyl group:
(CH3)3C__y ~ H-Y + (CH3)2=CH2 The trialkylsilyl group is especially efficient when the leaving group is fluorine, owing to the large enthalpy of f ormation of the Si-F bond.
When A is a proton, or a proton precursor such as a tertioalkyl radical, it is advantageous to conduct the reaction in the presence of a tertiary or hindered base. Examples, given without limiting the scope: of the invention, are: triethylamine, di-isopropylamine, quinuclidine, 1,4-diazobicyclo[2,2,2.]octane (DABCO); pyridine, alkylpyridines, dialkylaminopyridines; N-alkylimidazoles, imidazo[1,1-a]pyridine); amidines such as 1,5-diazabicyclo[4,3,0]non-5-ene (DBN), 1,8-diazat~icyclo[5,4,0]undec-7-ene (DBU); guanidines such as tetramethyl-guanidine, 1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine (HPP).
An M+ cation obtained by either of the processes described above, or any other process can be replaced by any other canon by techniques known to the man skilled in the art, for example by selective precipitation or solvent extraction, or with ion-exchange resins.
In several cases, th.e potassium salt of the compounds of the invention are insoluble or sparingly soluble in water and can be precipitated from this medium from the more soluble H+, Li+, or Na+~ salts and can be purified by recrystallization from this medium or its mixture with water miscible solvents such as acetonitrile, dioxane, acetone or THF, given here as non limiting examples.
Conversely, the Lithium salt can be obtained from the potassium salts by addition of a stoichiometric quaJntity of LiCI in THF where KCl is insoluble.
The allrylammonium salts, especially the tetraalkyl ammonium salts are usually insoluble in water and can be extracted from aqueous media by various solvents, including halogenated solvent such as. dichloromethane, dichloroethane, trichloromethane, trichloroethane, 1, l,1,2-tetrafluorof;thane . . .
Is it understood that any of the monomer functionality that could interfere with the reaction leading to the formation of the S02-Y-S02 bonds can be temporarily protected by techniques known to one skilled in the art. For example, the perfluorovinyl ether groups can be chlorinated, leading to the unreactive perhaloether; the perfluorovinyl ether being formed again in the presence of a reducing agent, such as zinc dust, zinc-copper bronze or tetrakis(dimethylamino)ethylene, or electrochemically.
The following e:~amples are given to illustrate some useful monomers of the invention illustrating those possessing a symmetrical form. It is understood that such compounds are not given to limit the scope of the invention, especially considering the various possible combinations of T' moieties:
or:
or:
or:
or M+
CF=CF2-O C F2- CF- O- CF2- C F2- S02- N- S02- C F2- CF2 O- C F- C F2 O- CF=CF2 I I
X n X m M+
CF=CF2-O CF2- i F- O- CF2-CF2- S02- i- S02-CF2- CF2 O- i F-CF2 O- CF=CF2 X n H X m M+
CF=CF2-O CF2-CF-O-CF2-CF2-S02-C-S02-CF2-CF2 O-CF-CF2 O-CF=CF2 I I I
X n S02CF3 X m F~F F~F
M /'~+
F O CF2- iF-O-CF2-CF2-S02-N-S02-CF2-CF2 O- iF-CF2 O F
X n X m F~F F~F
M+
F O CF2- iF-O-CF2-CF2-S02- i-S02-CF2-CF2 O- iF-CF2 O F
X n Q X m or or or;
or:
where:
~ M+
CFy=CF -502- N-SOZ ~CF=CF2 ~ M+
CFZ=CF -502- C-SOZ ~CF=CFZ
D
~ M+
CFZ=CF- O~SOZ-N- SOZ ~O- CF=CFZ
~ M+
CF2=CF-O --( ( ) )--S02-C-SO Z --( ( J }--O-CF=CF Z
Q
- M+, Y have the above defined meaning;
- n or m, equal or different being comprised between 0 (included) and 10.
In practice, the ion-exchange membranes of the invention are obtained by homo-or co-polymerization of the bifunctional monomer described above. For copolymers, the comonomer are advantageouslw chosen among the monofunctional monomer salts of the general formula:
[T"-S03] - M+
where:
[T~~-S02-Y-S02-Q']- M+
- T" is identica to or different from T or T' and has the same definition;
- M+, Y have ~he above defined meaning;
- Q' identical or different than Q.
Non-limiting examples of such monofunctional monomers include:
CFZ=CF- O CFZ- i F-O CFZ- CFZ-S03 M+
X n or:
or:
or or:
or:
or:
or or:
or:
M+
CF2=CF- O CF2-CF-O CF2- CF2-S02- N- S02-R' X n M+
C F2=CF- O CF2-C F- O CF2- CF2- S02- C- S02- R' X n X
F~F
F O CF2- i F-O CF2- CF2-S03 M
X n FXF
M+
O CF2-CF-O CF2-CF2--S02-N-S02-R' X n F~F
M+
F O CF2-CF-O CF2- CF2-- S02- i - S02-R' X n Q
CF2=CF---t ( )}--S03 M+
~ M+
CF'2=CF S02- N- S02R' ~ M+
CF2=CF S02 i - S02 R' CF2=CF- O-( ( ) j-- S02-M+
or or:
or or or ~ M+
CF2=CF-O---(( )J'-'S02-~-SOZR' D
C:F=CF2- O CFZ- ~F-O CFZ-(CFz)P- COZ M+
X n F~F
F O CF2- iF-O CF2-(CF2)P-C02-M
X n CiF2=CF--( ( )}-COZ M+
CI=2=CF-O~COZ M+
where:
0>_p>_2 Advantageously, the polymerization or co-polymerization reactions are conducted in a solvent of the monomers. The monomers are essentially very soluble in most common polar solvents.
These include as non limiting examples: water, lower aliphatic alcohols, acetone, methyl-ethylketone, cycli~;, ketones, ethylene and propylene carbonates, 'y-butyrolactone, the glymes, N-alkyl-pyrrolidones, methylene chloride, chloroform, 1,2-dichloroethane, N-alkylimidazole, fluoroalkanes or mixtures thereof... Furthermore the choice of M allows to optimize the solubility of the monomers, through specific cation-solvent interactions. It is understood for one skilled in the ,art that after the polymerization is completed, M exchange can take place by conventional techluques used fox ion-exchange resins, more easily so due to the cross-linked nature of the final material and the rapid diffusion of ionic species.
Solid additives, usually in the form of powders or fibers, either inorganic or organic can be added at the fabrication stage in order to improve the mechanical properties, to act as pore forming agents or ;as support for the catalyst (e.g. platinum deposited on carbon particles}.
Description of Invention:
Departing from prior art, we describe here the use of perfluoro-bis(vinylethers) having the highly dissociated imide, bis(sulfonylinethane) or tris(sulfonylmethane)ionic groups, as a base for crosslinked ion-exchange membranes directly obtained in their final shape (usually filins, or hollow tubes and referred thereafter as membranes) and having a high density of ionic functions. The polymerization can be carried out in concentrated solution of the monomer in its salt form. The materials thus obtained do not have the disadvantages of the previously known perfluorinated ionomers, i.e. they are dimensionally stable in the presence of all solvents, including water, yc;t are highly conductive due to the high concentration of ionic groups; the crosslinks form an excellent barner to both oxygen and methanol or other organic fuels. No ThE is necessary in the polymerization process, thereby reducing hazards. The materials can be processed into extremely thin membranes and are thus cost efficient in terms of the utilization of the monomers. Furthermore, it is easy to include the electrode materials at one or both sides of the membrane ~3uring its fabrication, either at the stage of monomer polymerization or to coat them from a slurry of the active materials in a solution of the monomer in an appropriate solvent applied to an already formed membrane and subsequent polymerization.
Besides, the strong electron withdrawing nature of the imide, polysulfonyl substituted carbanions as well as the perfluorosulfonate anion enhances the catalytic activity of the cations M+ which are specific for many important reactions. The materials are thus useful as supported catalysts when in the form exchanged with an active M+ cation. In the form of a crosslinlced material, the catalyst is easily separated mechanically from the reaction medium. Non-limiting examples of reactiions which can be catalyzed include Diels & Alder additions, Friedel & Craft reactions, aldol condensations, cationic polymerization, esterifications, acetal formation.
The bifunctional monomers of the present invention have the general formula:
~ T-S02-Y-S02T~ ~_ M+
where T or T', identical or different represent a polymerization-active radical. As examples, the T moieties is advantageously chosen among the following radicals:
F2C= Cf=- O CF2 ~F- CF Z- CFZ
X n or:
F~ F
O O
CFZ-CF-O CFZ-CFZ-X n or:
CZZ=CZ- E
denoted as:
CZ2=CZ- E
CZZ=CZ- E
E- CZ=CZZ
where:
- X represents F, Cl or CF3 - n is an integer comprised between 0 (zero) (included) and 10 - IT represents N (nitrogen), CH, CQ
- Q represents an alkyl or alkylene with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents, or T or an alkyl or alkylene sulfonyl group, with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents - E represents an ether -O-, sulfide -S-, sulfone -S02- or nothing (direct =C(Z)-aryl link).
- Z is either F ~or H.
The monomers according to the invention can be obtained by different processes. In a simple embodiment, the irnide type monomers are obtained by the following reactions:
2TS02-L + [A2N]-M+ -~ 2LA + (TS02)2N-M+
or TS02-L + [T'AN]-M+ --~ LA + [(TS02)N(S02T')]'M+
T and T', identical or different corresponding to the above definition.
Sinularly, the carb~~n-based compounds results from similar reactions:
2TS02-L + [A2CQ]-M+ ~ 2LA + [(TS02)2CQ-]M+
or:
2TS02-L + [A2CQ]-M+ -~ 2LA + [(TS02)2CQ-]M+
- L being a learning group, like an halogen, F, Cl, Br, a pseudo halogen like SCN, or an electrophilic heteroatom moieties, like N-imidazolyl, N-triazolyl, or RS02-O-, R
represents an alkyl or alkylene with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents, or T.
A represents. an M+ cation ( 1/mMm+) cation, including trialkylsilyl group, trialkylstannyl groups or tertioallryl as a proton equivalent, in which the alkyl substituents comprise from 1 to 6 carbon atoms. As example, the reaction of lithium nitride on a sufonyl fluoride may be mentioned:
2TS02F ~- Li3N --~ 2LiF + [(TS02)2N]-Li+
A is advantageously a tertioalkyl radical as this group is a precursor to a proton with the driving force being the formation of an alkene; as for instance in the case of the tertiobutyl group:
(CH3)3C__y ~ H-Y + (CH3)2=CH2 The trialkylsilyl group is especially efficient when the leaving group is fluorine, owing to the large enthalpy of f ormation of the Si-F bond.
When A is a proton, or a proton precursor such as a tertioalkyl radical, it is advantageous to conduct the reaction in the presence of a tertiary or hindered base. Examples, given without limiting the scope: of the invention, are: triethylamine, di-isopropylamine, quinuclidine, 1,4-diazobicyclo[2,2,2.]octane (DABCO); pyridine, alkylpyridines, dialkylaminopyridines; N-alkylimidazoles, imidazo[1,1-a]pyridine); amidines such as 1,5-diazabicyclo[4,3,0]non-5-ene (DBN), 1,8-diazat~icyclo[5,4,0]undec-7-ene (DBU); guanidines such as tetramethyl-guanidine, 1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine (HPP).
An M+ cation obtained by either of the processes described above, or any other process can be replaced by any other canon by techniques known to the man skilled in the art, for example by selective precipitation or solvent extraction, or with ion-exchange resins.
In several cases, th.e potassium salt of the compounds of the invention are insoluble or sparingly soluble in water and can be precipitated from this medium from the more soluble H+, Li+, or Na+~ salts and can be purified by recrystallization from this medium or its mixture with water miscible solvents such as acetonitrile, dioxane, acetone or THF, given here as non limiting examples.
Conversely, the Lithium salt can be obtained from the potassium salts by addition of a stoichiometric quaJntity of LiCI in THF where KCl is insoluble.
The allrylammonium salts, especially the tetraalkyl ammonium salts are usually insoluble in water and can be extracted from aqueous media by various solvents, including halogenated solvent such as. dichloromethane, dichloroethane, trichloromethane, trichloroethane, 1, l,1,2-tetrafluorof;thane . . .
Is it understood that any of the monomer functionality that could interfere with the reaction leading to the formation of the S02-Y-S02 bonds can be temporarily protected by techniques known to one skilled in the art. For example, the perfluorovinyl ether groups can be chlorinated, leading to the unreactive perhaloether; the perfluorovinyl ether being formed again in the presence of a reducing agent, such as zinc dust, zinc-copper bronze or tetrakis(dimethylamino)ethylene, or electrochemically.
The following e:~amples are given to illustrate some useful monomers of the invention illustrating those possessing a symmetrical form. It is understood that such compounds are not given to limit the scope of the invention, especially considering the various possible combinations of T' moieties:
or:
or:
or:
or M+
CF=CF2-O C F2- CF- O- CF2- C F2- S02- N- S02- C F2- CF2 O- C F- C F2 O- CF=CF2 I I
X n X m M+
CF=CF2-O CF2- i F- O- CF2-CF2- S02- i- S02-CF2- CF2 O- i F-CF2 O- CF=CF2 X n H X m M+
CF=CF2-O CF2-CF-O-CF2-CF2-S02-C-S02-CF2-CF2 O-CF-CF2 O-CF=CF2 I I I
X n S02CF3 X m F~F F~F
M /'~+
F O CF2- iF-O-CF2-CF2-S02-N-S02-CF2-CF2 O- iF-CF2 O F
X n X m F~F F~F
M+
F O CF2- iF-O-CF2-CF2-S02- i-S02-CF2-CF2 O- iF-CF2 O F
X n Q X m or or or;
or:
where:
~ M+
CFy=CF -502- N-SOZ ~CF=CF2 ~ M+
CFZ=CF -502- C-SOZ ~CF=CFZ
D
~ M+
CFZ=CF- O~SOZ-N- SOZ ~O- CF=CFZ
~ M+
CF2=CF-O --( ( ) )--S02-C-SO Z --( ( J }--O-CF=CF Z
Q
- M+, Y have the above defined meaning;
- n or m, equal or different being comprised between 0 (included) and 10.
In practice, the ion-exchange membranes of the invention are obtained by homo-or co-polymerization of the bifunctional monomer described above. For copolymers, the comonomer are advantageouslw chosen among the monofunctional monomer salts of the general formula:
[T"-S03] - M+
where:
[T~~-S02-Y-S02-Q']- M+
- T" is identica to or different from T or T' and has the same definition;
- M+, Y have ~he above defined meaning;
- Q' identical or different than Q.
Non-limiting examples of such monofunctional monomers include:
CFZ=CF- O CFZ- i F-O CFZ- CFZ-S03 M+
X n or:
or:
or or:
or:
or:
or or:
or:
M+
CF2=CF- O CF2-CF-O CF2- CF2-S02- N- S02-R' X n M+
C F2=CF- O CF2-C F- O CF2- CF2- S02- C- S02- R' X n X
F~F
F O CF2- i F-O CF2- CF2-S03 M
X n FXF
M+
O CF2-CF-O CF2-CF2--S02-N-S02-R' X n F~F
M+
F O CF2-CF-O CF2- CF2-- S02- i - S02-R' X n Q
CF2=CF---t ( )}--S03 M+
~ M+
CF'2=CF S02- N- S02R' ~ M+
CF2=CF S02 i - S02 R' CF2=CF- O-( ( ) j-- S02-M+
or or:
or or or ~ M+
CF2=CF-O---(( )J'-'S02-~-SOZR' D
C:F=CF2- O CFZ- ~F-O CFZ-(CFz)P- COZ M+
X n F~F
F O CF2- iF-O CF2-(CF2)P-C02-M
X n CiF2=CF--( ( )}-COZ M+
CI=2=CF-O~COZ M+
where:
0>_p>_2 Advantageously, the polymerization or co-polymerization reactions are conducted in a solvent of the monomers. The monomers are essentially very soluble in most common polar solvents.
These include as non limiting examples: water, lower aliphatic alcohols, acetone, methyl-ethylketone, cycli~;, ketones, ethylene and propylene carbonates, 'y-butyrolactone, the glymes, N-alkyl-pyrrolidones, methylene chloride, chloroform, 1,2-dichloroethane, N-alkylimidazole, fluoroalkanes or mixtures thereof... Furthermore the choice of M allows to optimize the solubility of the monomers, through specific cation-solvent interactions. It is understood for one skilled in the ,art that after the polymerization is completed, M exchange can take place by conventional techluques used fox ion-exchange resins, more easily so due to the cross-linked nature of the final material and the rapid diffusion of ionic species.
Solid additives, usually in the form of powders or fibers, either inorganic or organic can be added at the fabrication stage in order to improve the mechanical properties, to act as pore forming agents or ;as support for the catalyst (e.g. platinum deposited on carbon particles}.
Claims
1) Di-functional monomers of general formula where:
- T or T' are identical or different and each represent an organic radical having at least one polymerization-active function;
- M~ represents a cation, inorganic or organic, preferably chosen among: H+, Li+, Na+, K+, 1/2Mg2+, 1/2Ca2+, 1/2Ba2+, 1/2Zn2+ and other transition metals, 1/3La3+
and other rare earths, ammonium, amidinium, pyridinium, imidazolium, guanidinium, sulfonium, phosphonium, iodonium, organometallic canons, all possibly including coordination ligands....
- Y represent, N (nitrogen), CH, or CQ.
- Q represents an alkyl or alkylene with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents, or T or an alkyl- or an alkylene- sulfonyl group, with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents.
2) Di-functional monomers according to claim 1 characterized in that T is chosen among:
or:
or: or: where:
- X represents F, Cl or CF3 - n or m, equal or different being comprised between 0 (included) and 10 - E represents an ether -O-, sulfide -S-, sulfone -SO2- or nothing (direct =C(Z)~aryl link) - Z is either F or H.
3) Crosslinked ion exchange materials and solid ion conductor characterized in that they are prepared using a di-functional monomer according to claims 1 and 2.
4) Crosslinked ion exchange materials and solid ion conductor according to claim 3 characterized in that the di-functional monomer is:
or: or mixtures thereof.
5) Crosslinked ion exchange materials and solid ion conductor according to claim 3 characterized in that the di-functional monomer is:
or:
or mixtures thereof 6) Crosslinked ion exchange materials and solid ion conductor according to claims 1 to 5 characterized in that the di-functional monomer is copolymerized with at least one monofunctional monomer 7) Crosslinked ion exchange materials and solid ion conductor according to claim 6 characterized in that at least one of the monofunctional monomers has the following structure:
or:
T"' identical or different from T and T' and has the same definition as T or T' in claim 1.
8) Crosslinked ion exchange materials and solid ion conductor according to claim 6 characterized in that at least one of the monofunctional monomer has the following structure:
CF2=CF-O-CF2-CF2-SO3-M+
or: ar mixtures thereof.
9) Crosslinked ion exchange materials and solid ion conductor according to claim 6 characterized in that at least one of the monofunctional monomer has the following structure:
or:
or mixtures thereof.
10) Crosslinked ion exchange materials and solid ion conductor according to claims 3 to 6 characterized in that at least one of the monofunctional monomer has the following structure:
or:
where:
p= 1 or 2 or:
or:
or:
or: R' 11) Method for preparing the material according to claims 3 to 6 characterized in that the monomers or the mixture of monomers are polymerized in solution in a suitable solvent or mixture of solvents.
12) Method for preparing the material according to claims 3 to 6 in useful shape, especially thin films membranes or hollow tubes (hereinafter referred to as membranes) characterized in that the monomers or the mixture of monomers in solution in a suitable solvent or mixture of solvents are coated, printed, silkscreened or extruded with or without a removable support web and then polymerized.
13) Method for preparing the material according to claims 3 to 6 in the form of beads or latex characterized in that the monomers or the mixture of monomers are polymerized as an emulsion in suitable non-miscible solvents.
14) Method for preparing thin membrane according to claim 11 characterized in that the suitable solvent is chosen among: water, lower aliphatic alcohols, acetone, methyl-ethylketone, cyclic ketones, ethylene and propylene carbonates, g-butyrolactone, the glymes, N-allryl-pyrolidones, tetraalkylsulfamides, methylene chloride, chloroform, 1,2 dichloroethane, N-alkylimidazole, fluorinated hydrocarbons and mixtures thereof.
15) Method for preparing material according to claim 3 to 6 characterized in that a radical polymerization initiator is added to the solution of monomers in suitable solvents.
16) Method for preparing material according to claim 15 characterized in that the radical polymerization initiator is thermally activated.
17) Method for preparing material according to claim 15 characterized in that the radical polymerization initiator is a peroxide or an azo compound.
18) Method for preparing material according to claim 15 characterized in that the radical polymerization initiator is activated by actinic radiation.
19) Method for preparing material according to claim 3 to 6 characterized in that ion exchange to the desired canon M+ is performed after polymerization.
20) Material according to claim 3 to 6 characterized in that inorganic or organic filler particles, including fibers woven or non woven cloth , are added to the solution before polymerization.
21)Electrochemical cell characterized in that a membrane according to claims 3 to 20 is used as solid electrolyte.
22) Electrochemical cell according to claim 21 characterized in that it is a fuel cell, and / or a water electrolyser, a chlor-alkali cell, an electrochemical acid or salt recovery cell, an ozone producing cell.
23) Electrochemical cell according to claim 21 characterized in that at least one electrode is in contact with the membrane.
24) Electrochemical cell according to claims 23 characterized in that at least one electrode contains a conductive additive, optionally a catalyst, and optionally a pore forming agent and the monomers of claims 1 to 6 is coated on the electrolyte membrane then polymerized.
25) Electrochemical cell according to claim 23 characterized in that at least one electrode contains a conductive additive, a catalyst, and optionally a pore forming agent, and the monomers of claims 1 and 3 are coated thereon, or co-extruded with, the electrolyte membrane before polymerization of the latter and the whole assembly is then polymerized.
26) Electrochemical cell according to claim 23 characterized in that it forms the element of a fuel cell where M+ is an hydrated proton and the positive electrode contains an oxygen reduction catalyst and the negative electrode contains either an hydrogen, methanol, dimethoxymethane, trimethoxymethane, trioxane or ammonia oxidation catalyst.
27) Fuel cell according to claim 26 characterized in that the electrodes are applied onto the membrane using the process or either claims 23 to 25 28) Material according to claims 3 to 13 characterized in that it is used for chlor-alkali electrolysis.
29) Material according to claims 3 to 13 characterized in that it is used as a separator in the electrochemical preparation of organic or inorganic substances.
31) Material according to claims 3 to 13 and 20 characterized in that it is used a separator between an adueous phase and an organic phase.
32) Material according to claims 3 to 13 and 13 characterized in that the M+
ions associated with the non-nucleophilic anionic centers of the backbone confer catalytic properties.
33) Material according to claim 32 characterized in that it is a catalyst for Diels & Alder additions, Friedel & Craft reactions, aldol condensations, cationic polymerization, esterifications, acetal formation.
- T or T' are identical or different and each represent an organic radical having at least one polymerization-active function;
- M~ represents a cation, inorganic or organic, preferably chosen among: H+, Li+, Na+, K+, 1/2Mg2+, 1/2Ca2+, 1/2Ba2+, 1/2Zn2+ and other transition metals, 1/3La3+
and other rare earths, ammonium, amidinium, pyridinium, imidazolium, guanidinium, sulfonium, phosphonium, iodonium, organometallic canons, all possibly including coordination ligands....
- Y represent, N (nitrogen), CH, or CQ.
- Q represents an alkyl or alkylene with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents, or T or an alkyl- or an alkylene- sulfonyl group, with 1 to 20 carbons, halogenated or not, possibly having aza or oxa substituents.
2) Di-functional monomers according to claim 1 characterized in that T is chosen among:
or:
or: or: where:
- X represents F, Cl or CF3 - n or m, equal or different being comprised between 0 (included) and 10 - E represents an ether -O-, sulfide -S-, sulfone -SO2- or nothing (direct =C(Z)~aryl link) - Z is either F or H.
3) Crosslinked ion exchange materials and solid ion conductor characterized in that they are prepared using a di-functional monomer according to claims 1 and 2.
4) Crosslinked ion exchange materials and solid ion conductor according to claim 3 characterized in that the di-functional monomer is:
or: or mixtures thereof.
5) Crosslinked ion exchange materials and solid ion conductor according to claim 3 characterized in that the di-functional monomer is:
or:
or mixtures thereof 6) Crosslinked ion exchange materials and solid ion conductor according to claims 1 to 5 characterized in that the di-functional monomer is copolymerized with at least one monofunctional monomer 7) Crosslinked ion exchange materials and solid ion conductor according to claim 6 characterized in that at least one of the monofunctional monomers has the following structure:
or:
T"' identical or different from T and T' and has the same definition as T or T' in claim 1.
8) Crosslinked ion exchange materials and solid ion conductor according to claim 6 characterized in that at least one of the monofunctional monomer has the following structure:
CF2=CF-O-CF2-CF2-SO3-M+
or: ar mixtures thereof.
9) Crosslinked ion exchange materials and solid ion conductor according to claim 6 characterized in that at least one of the monofunctional monomer has the following structure:
or:
or mixtures thereof.
10) Crosslinked ion exchange materials and solid ion conductor according to claims 3 to 6 characterized in that at least one of the monofunctional monomer has the following structure:
or:
where:
p= 1 or 2 or:
or:
or:
or: R' 11) Method for preparing the material according to claims 3 to 6 characterized in that the monomers or the mixture of monomers are polymerized in solution in a suitable solvent or mixture of solvents.
12) Method for preparing the material according to claims 3 to 6 in useful shape, especially thin films membranes or hollow tubes (hereinafter referred to as membranes) characterized in that the monomers or the mixture of monomers in solution in a suitable solvent or mixture of solvents are coated, printed, silkscreened or extruded with or without a removable support web and then polymerized.
13) Method for preparing the material according to claims 3 to 6 in the form of beads or latex characterized in that the monomers or the mixture of monomers are polymerized as an emulsion in suitable non-miscible solvents.
14) Method for preparing thin membrane according to claim 11 characterized in that the suitable solvent is chosen among: water, lower aliphatic alcohols, acetone, methyl-ethylketone, cyclic ketones, ethylene and propylene carbonates, g-butyrolactone, the glymes, N-allryl-pyrolidones, tetraalkylsulfamides, methylene chloride, chloroform, 1,2 dichloroethane, N-alkylimidazole, fluorinated hydrocarbons and mixtures thereof.
15) Method for preparing material according to claim 3 to 6 characterized in that a radical polymerization initiator is added to the solution of monomers in suitable solvents.
16) Method for preparing material according to claim 15 characterized in that the radical polymerization initiator is thermally activated.
17) Method for preparing material according to claim 15 characterized in that the radical polymerization initiator is a peroxide or an azo compound.
18) Method for preparing material according to claim 15 characterized in that the radical polymerization initiator is activated by actinic radiation.
19) Method for preparing material according to claim 3 to 6 characterized in that ion exchange to the desired canon M+ is performed after polymerization.
20) Material according to claim 3 to 6 characterized in that inorganic or organic filler particles, including fibers woven or non woven cloth , are added to the solution before polymerization.
21)Electrochemical cell characterized in that a membrane according to claims 3 to 20 is used as solid electrolyte.
22) Electrochemical cell according to claim 21 characterized in that it is a fuel cell, and / or a water electrolyser, a chlor-alkali cell, an electrochemical acid or salt recovery cell, an ozone producing cell.
23) Electrochemical cell according to claim 21 characterized in that at least one electrode is in contact with the membrane.
24) Electrochemical cell according to claims 23 characterized in that at least one electrode contains a conductive additive, optionally a catalyst, and optionally a pore forming agent and the monomers of claims 1 to 6 is coated on the electrolyte membrane then polymerized.
25) Electrochemical cell according to claim 23 characterized in that at least one electrode contains a conductive additive, a catalyst, and optionally a pore forming agent, and the monomers of claims 1 and 3 are coated thereon, or co-extruded with, the electrolyte membrane before polymerization of the latter and the whole assembly is then polymerized.
26) Electrochemical cell according to claim 23 characterized in that it forms the element of a fuel cell where M+ is an hydrated proton and the positive electrode contains an oxygen reduction catalyst and the negative electrode contains either an hydrogen, methanol, dimethoxymethane, trimethoxymethane, trioxane or ammonia oxidation catalyst.
27) Fuel cell according to claim 26 characterized in that the electrodes are applied onto the membrane using the process or either claims 23 to 25 28) Material according to claims 3 to 13 characterized in that it is used for chlor-alkali electrolysis.
29) Material according to claims 3 to 13 characterized in that it is used as a separator in the electrochemical preparation of organic or inorganic substances.
31) Material according to claims 3 to 13 and 20 characterized in that it is used a separator between an adueous phase and an organic phase.
32) Material according to claims 3 to 13 and 13 characterized in that the M+
ions associated with the non-nucleophilic anionic centers of the backbone confer catalytic properties.
33) Material according to claim 32 characterized in that it is a catalyst for Diels & Alder additions, Friedel & Craft reactions, aldol condensations, cationic polymerization, esterifications, acetal formation.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002228466A CA2228466A1 (en) | 1998-01-30 | 1998-01-30 | New improved ion exchange membranes, their methods of preparation and their uses |
| DE69908499T DE69908499T2 (en) | 1998-01-30 | 1999-01-29 | POLYMERIZABLE BIS-SULFONYL DERIVATIVES AND THEIR USE IN THE MANUFACTURE OF ION EXCHANGE MEMBRANES |
| JP53875099A JP5073883B2 (en) | 1998-01-30 | 1999-01-29 | Crosslinkable bisulfonyl derivatives and their use for the production of ion exchange membranes |
| CA2283132A CA2283132C (en) | 1998-01-30 | 1999-01-29 | Crosslinkable bi-sulphonyl derivatives and their uses for preparing ion-exchanging membranes |
| PCT/CA1999/000083 WO1999038842A1 (en) | 1998-01-30 | 1999-01-29 | Crosslinkable bi-sulphonyl derivatives and their uses for preparing ion-exchanging membranes |
| EP99903551A EP0973734B1 (en) | 1998-01-30 | 1999-01-29 | Crosslinkable bi-sulphonyl derivatives and their uses for preparing ion-exchanging membranes |
| EP03004041A EP1312603A1 (en) | 1998-01-30 | 1999-01-29 | Polymerisable bis-sulphonyl derivatives and their use for preparing ion exchange membranes |
| US10/200,528 US20030023016A1 (en) | 1998-01-30 | 2002-07-23 | Cross-linkable bi-sulphonyl derivatives and their uses for preparing ion-exchanging membranes |
| US10/858,208 US20050014917A1 (en) | 1998-01-30 | 2004-06-02 | Cross-linkable bi-sulphonyl derivatives and their uses for preparing ion-exchanging membranes |
| US12/146,903 US8697824B2 (en) | 1998-01-30 | 2008-06-26 | Cross-linkable bi-sulphonyl derivatives and their uses for preparing ion-exchanging membranes |
| JP2010068974A JP2010248499A (en) | 1998-01-30 | 2010-03-24 | Cross-linkable bisulphonyl derivative and use thereof for preparing ion-exchanging membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002228466A CA2228466A1 (en) | 1998-01-30 | 1998-01-30 | New improved ion exchange membranes, their methods of preparation and their uses |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2228466A1 true CA2228466A1 (en) | 1999-07-30 |
Family
ID=29409200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002228466A Abandoned CA2228466A1 (en) | 1998-01-30 | 1998-01-30 | New improved ion exchange membranes, their methods of preparation and their uses |
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| Country | Link |
|---|---|
| CA (1) | CA2228466A1 (en) |
-
1998
- 1998-01-30 CA CA002228466A patent/CA2228466A1/en not_active Abandoned
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