CA2228467A1 - New techniques and processes for crosslinking ion exchange membranes and their applications - Google Patents
New techniques and processes for crosslinking ion exchange membranes and their applications Download PDFInfo
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- CA2228467A1 CA2228467A1 CA 2228467 CA2228467A CA2228467A1 CA 2228467 A1 CA2228467 A1 CA 2228467A1 CA 2228467 CA2228467 CA 2228467 CA 2228467 A CA2228467 A CA 2228467A CA 2228467 A1 CA2228467 A1 CA 2228467A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
- C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
Crosslinking sulfonated polymers through sulfonimide, bis(sulfonylmethane) or tris(sulfonylmethane) chains containing an ionic charge.
Description
New Techniques and Processes for Crosslinking Ion Exchange Membranes and their Applications This invention relates to techniques and process for crosslinking ion exchange membranes and their applications.
Prior 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~, Dow~ or materials developed by Ballard Inc. (W097/25369) are copolymers of tetrafluoraethylene (TFE) and of perfluorovinylethers or trifluorovinylstryrene. The active monomers have chemical functionalities which are the precursors of ionic groups of the sulfonate or carboxylate type. These precursors are:
FZC=CF-O CFz- iF-O CFZ-CF2-S02F
X n or:
or FZC=CF-O CFZ-GF-O (CFZ~COZR
IX n FZC=CF ~S02F
Sulfonated polyaromatic imides or ether sulfones have also been considered as candidates:
0 0-(~- So - 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 the ionic form by hydrolysis (--S02F ~ -S03 M+; -C02R ~ - C02 M+)
Prior 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~, Dow~ or materials developed by Ballard Inc. (W097/25369) are copolymers of tetrafluoraethylene (TFE) and of perfluorovinylethers or trifluorovinylstryrene. The active monomers have chemical functionalities which are the precursors of ionic groups of the sulfonate or carboxylate type. These precursors are:
FZC=CF-O CFz- iF-O CFZ-CF2-S02F
X n or:
or FZC=CF-O CFZ-GF-O (CFZ~COZR
IX n FZC=CF ~S02F
Sulfonated polyaromatic imides or ether sulfones have also been considered as candidates:
0 0-(~- So - 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 the ionic form by hydrolysis (--S02F ~ -S03 M+; -C02R ~ - C02 M+)
-2-where:
- M+ represents a cation, with for example: H+, Li+, Na+, K+, l/2Mg2+, 1/2Ca2+, I/ZBa2+ and other alkaline earth metals ions, 1/2Zn2+, l/2Cu2+ and other transition metals ions, 1/3A13+, 1/3Fe3+, 1/3Sc3+, 1/3Y3+, 1/3La3+, and other rare earth metals ions, or an organic cation of the opium type, oxonium, 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 have 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, leave 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 under pressure and may 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;
- M+ represents a cation, with for example: H+, Li+, Na+, K+, l/2Mg2+, 1/2Ca2+, I/ZBa2+ and other alkaline earth metals ions, 1/2Zn2+, l/2Cu2+ and other transition metals ions, 1/3A13+, 1/3Fe3+, 1/3Sc3+, 1/3Y3+, 1/3La3+, and other rare earth metals ions, or an organic cation of the opium type, oxonium, 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 have 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, leave 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 under pressure and may 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/gram 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;
1), resulting in typically less than 1 milli-equivalent/gram 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 cells (DMFC's).
Non fluorinated systems like sulfonated polyimides or polyether sulfones, proposed as substitute for the fluorinated material, suffer from the same difficulty in compromising between the charge density, thus conductivity and the solubility or excessive swelling.
Description of Invention While it is known in that art that perfluoropolymers usually cannot be crosslinked by the techniques usually employed with non fluorinated polymers, the present invention describes a novel general technique for creating crosslinks between sulfonyl groups attached to polymers including those having a perfluorinated backbone, as for example derived from the monomer (I) and its copolymers. Advantageously, the crosslinking can be achieved after the polymer has been processed while in the processable non ionic precursor form. The invention also relates to the use of the crosslinked shaped material in membrane form for applications including fuel cells, water electrolysis, chlor-alkali process, electrosynthesis, water treatment and ozone production.
The creation of stable crosslinks is achieved through the reaction of two -from adjacent chains to form the sulfonimide, bis(sulfonylinethane) or tris sulfonylinethane derivatives, schematized as:
S02L + LS02 A2Y-(M+) f S02-~ S02 + 2 LA
SOIL + LS02 L(M+)-YS02Y-(M+)L
i S0 2 YSO 21f- SOZ
M+ M+
+ 2 LA
S02L + LS02 A(M+rYS02QS02Y-(M+~1 o i o sot Yso2QSO2Y-sot M+ M
+ 2 u~
where M has the above meaning and Y represents:
- N (Nitrogen) - CH, CQ where Q represents a monovalent, possibly fluorinated or perfluorinated alkyl, oxaalkyl, azaalkyl, aryl or arylalkyl or alkylaryl radical containing 2 to 20 carbon atoms, S02R CCN, CF
A = M or Si(R)3, Ge(R')3, Sn(R')3, (R' = alkyl from 1 to 18 carbon atoms) Q = a divalent, preferably halogenated, especially perfluorinated alkyl, oxaalkyl, azaalkyl, aryl or arylalkyl radical containing 0 to 20 carbon atoms when there is no carbon atom, the compound is a sulfamide...
The M+ species may themselves be solvated or complexed to increase their solubility or reactivity. For example, protons can be complexed by a strong nucelophilic tertiary base like triethylamine (TEA), dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2.2.2~octane or as nascent form in the tertiobutyl radical dispxoportionating readily into an ether, H and CH2=C(CH3)3, metallic ions are solvated by dialkylethers or oligo-ethylene glycols or permethylated oligo-ethylendiamines (e.g. tetramethyl-ethylene diamine TMEDA). Similarly, the A2Y-(M+) compound can be formed in situ in the presence of strong bases such as organometallic compounds with labile protons attached to the Y
radical.
Suitable reagents include organo lithium, magnesium or aluminium compounds, especially their methyl derivatives which also serve as a source of carbon for Y =
CH, alkali metal amides as a source of nitrogen for Y = N, dialkyl amides like LDA (lithium diisopropylamide).
An advantage of the technique and materials of the invention is that the crosslinking agent creates ionophoretic, i.e. charged species, the negatively charged moieties being attached to the polymer and used as bridges between chains. It is known that the sulfonylimide groups and di or trisulfonylmethane groups are strong electrolytes in most media and thus the crosslinking reaction, in addition to improving the mechanical properties, has no detrimental effect on the conductivity and often results in its enhancement. The compounds whose formulae are given below are examples only of suitable ionogen crosslinking agents and are given to illustrate the principle of the invention:
O~~'Q + Oz(z3~Z3~ZOS3) -.
d3.1. + Z~Z~~ZOS3)Z(al~P~~)ZOS 0~8t~a + ZI~zOS
:uor~uanm a~ ~o adoos a~ ~~j o~ papua~m you aye ~nq uoRuanut a~ ~o aldtouud a~ a~~.~sn~ o~ uann are pine s~ua~~ ~unjuijsso~a ua~ouoi aiqu~ms ~o saldurexa a.ie nnojaq uann are a~ejnuuo~ asoc~nn spunodu~oa auZ
y~ Z +
+W +W
SOS OzOS~OS~ SOS
l Z OSOz OSl +W +W
zOSJll1 VAzOS
O ~ _ ~ Z+
+W +W
z OS _ ~zOS~ ?OS
___ l OSl +W + +W
zOSO VO OS
ae pazu~emauas si as~a snp m auiaqas le.~aua~ a~ 'aptuze a~n~usqns ~e ~o~ s~e '.~osmaa.~d .zaurAjod a~ uo ~p~a.~ si dno.~ ~ act uaqnn aaejd axed u~a uoyaea.z ~unluqsso,~a ~
'~ijanr~euza~~
Oz{z3~z3~ZOSNI(H~)!Sl(!'I)?
zfz3~zOSN(H~)!S(!'I))z3~z{z~~zOSNI(H~)!Sl(!'I)}zdJz{zOSN(r1U(H~)!Sl}
}I '~N '!'7ZHN ft~(H~) rIH~
-ZOSzfN($W)(da~l.lJ1zOSz{N(~'1)fiS(H~)l} ~3,L~+zHNZOSZHN
t''3.1.+zHN~(H~) zUdQ3W,IJ!'-I1I!S(H~)I~zOS~~OJBda+HN
X 'EN '!'INzIIS(H~)1rf'o'~ NrI
'S' 0~-i0-866l G9b8ZZZ0 ~a y The crosslinking reaction may imply the totality of the sulfonyl groups or a fraction of them. The crosslinking reagents may be applied by different techniques which are known to one skilled in the art. Conveniently, the processable thermoplastic or soluble material is shaped to the desired final form before crosslinking, e. g. membranes or hollow tubes and the material is brought in contact, by immersion or coating with a solution of the crosslinking reagent in a solvent which is non reactive towards the reactants. Appropriate solvents include but are not limited to polyhalocarbons, THF, the glymes, tertiary alkylamides including DMF, N methyl-pyrrolidone, tetraethyl urea and its cyclic analogs, N-alkyl-imidazoles, tetraalkyl sulfamides. The desired degree of crosslinking may be controlled by several factors such as time of contact, temperature or the concentration of the crosslinking reagent.
Alternatively, a latex of the processable material is intimately mixed with the reagent in solid form and the mixture is pressed or hot rolled, possibly in the presence of a non-solvent fluid such as an hydrocarbon. This technique is applicable in particular to thin membrane and results in high productivity though less homogeneous material is produced. It is understood that fillers such as powders, woven or non-woven fibers or filaments, can be added to the polymers before the crosslinking reaction as reinforcing agents.
If only a fraction of bridging bonds are required, the remaining -S02Y can be transformed into the ionic sulfonate form by alkaline hydrolysis.
Alternatively, the -S03M group or the non crosslinking imide group -S02NS02RFM can be obtained in the same conditions as for the crosslinks by ionogen reagents like respectively M+[{CH3)3Si0]- or M+[(CH3)3SiNS02RF]-; such examples are given for illustration but are not limitative. It may be advantageous to treat the membrane either sequentially by the crosslinking agent than by the non crosslinking ionogen reagents. Alternatively, the ionogen crosslinking agent and the non crosslinking ionogen are mixed together or codissolved in the solvent in predetermined proportions and react simultaneously.
The crosslinked material of the invention can be easily separated from the reactant products, which are either volatile like (CH3)3SiF or (CH3)3SiC1 or can be washed away in an appropriate solvent like water. Also, well known techniques from one skilled in the art like ion exchange or electrophoresis can be applied to exchange the cation M+ for the final application, (e.g. H+).
Non fluorinated systems like sulfonated polyimides or polyether sulfones, proposed as substitute for the fluorinated material, suffer from the same difficulty in compromising between the charge density, thus conductivity and the solubility or excessive swelling.
Description of Invention While it is known in that art that perfluoropolymers usually cannot be crosslinked by the techniques usually employed with non fluorinated polymers, the present invention describes a novel general technique for creating crosslinks between sulfonyl groups attached to polymers including those having a perfluorinated backbone, as for example derived from the monomer (I) and its copolymers. Advantageously, the crosslinking can be achieved after the polymer has been processed while in the processable non ionic precursor form. The invention also relates to the use of the crosslinked shaped material in membrane form for applications including fuel cells, water electrolysis, chlor-alkali process, electrosynthesis, water treatment and ozone production.
The creation of stable crosslinks is achieved through the reaction of two -from adjacent chains to form the sulfonimide, bis(sulfonylinethane) or tris sulfonylinethane derivatives, schematized as:
S02L + LS02 A2Y-(M+) f S02-~ S02 + 2 LA
SOIL + LS02 L(M+)-YS02Y-(M+)L
i S0 2 YSO 21f- SOZ
M+ M+
+ 2 LA
S02L + LS02 A(M+rYS02QS02Y-(M+~1 o i o sot Yso2QSO2Y-sot M+ M
+ 2 u~
where M has the above meaning and Y represents:
- N (Nitrogen) - CH, CQ where Q represents a monovalent, possibly fluorinated or perfluorinated alkyl, oxaalkyl, azaalkyl, aryl or arylalkyl or alkylaryl radical containing 2 to 20 carbon atoms, S02R CCN, CF
A = M or Si(R)3, Ge(R')3, Sn(R')3, (R' = alkyl from 1 to 18 carbon atoms) Q = a divalent, preferably halogenated, especially perfluorinated alkyl, oxaalkyl, azaalkyl, aryl or arylalkyl radical containing 0 to 20 carbon atoms when there is no carbon atom, the compound is a sulfamide...
The M+ species may themselves be solvated or complexed to increase their solubility or reactivity. For example, protons can be complexed by a strong nucelophilic tertiary base like triethylamine (TEA), dimethylaminopyridine (DMAP), 1,4-diazabicyclo[2.2.2~octane or as nascent form in the tertiobutyl radical dispxoportionating readily into an ether, H and CH2=C(CH3)3, metallic ions are solvated by dialkylethers or oligo-ethylene glycols or permethylated oligo-ethylendiamines (e.g. tetramethyl-ethylene diamine TMEDA). Similarly, the A2Y-(M+) compound can be formed in situ in the presence of strong bases such as organometallic compounds with labile protons attached to the Y
radical.
Suitable reagents include organo lithium, magnesium or aluminium compounds, especially their methyl derivatives which also serve as a source of carbon for Y =
CH, alkali metal amides as a source of nitrogen for Y = N, dialkyl amides like LDA (lithium diisopropylamide).
An advantage of the technique and materials of the invention is that the crosslinking agent creates ionophoretic, i.e. charged species, the negatively charged moieties being attached to the polymer and used as bridges between chains. It is known that the sulfonylimide groups and di or trisulfonylmethane groups are strong electrolytes in most media and thus the crosslinking reaction, in addition to improving the mechanical properties, has no detrimental effect on the conductivity and often results in its enhancement. The compounds whose formulae are given below are examples only of suitable ionogen crosslinking agents and are given to illustrate the principle of the invention:
O~~'Q + Oz(z3~Z3~ZOS3) -.
d3.1. + Z~Z~~ZOS3)Z(al~P~~)ZOS 0~8t~a + ZI~zOS
:uor~uanm a~ ~o adoos a~ ~~j o~ papua~m you aye ~nq uoRuanut a~ ~o aldtouud a~ a~~.~sn~ o~ uann are pine s~ua~~ ~unjuijsso~a ua~ouoi aiqu~ms ~o saldurexa a.ie nnojaq uann are a~ejnuuo~ asoc~nn spunodu~oa auZ
y~ Z +
+W +W
SOS OzOS~OS~ SOS
l Z OSOz OSl +W +W
zOSJll1 VAzOS
O ~ _ ~ Z+
+W +W
z OS _ ~zOS~ ?OS
___ l OSl +W + +W
zOSO VO OS
ae pazu~emauas si as~a snp m auiaqas le.~aua~ a~ 'aptuze a~n~usqns ~e ~o~ s~e '.~osmaa.~d .zaurAjod a~ uo ~p~a.~ si dno.~ ~ act uaqnn aaejd axed u~a uoyaea.z ~unluqsso,~a ~
'~ijanr~euza~~
Oz{z3~z3~ZOSNI(H~)!Sl(!'I)?
zfz3~zOSN(H~)!S(!'I))z3~z{z~~zOSNI(H~)!Sl(!'I)}zdJz{zOSN(r1U(H~)!Sl}
}I '~N '!'7ZHN ft~(H~) rIH~
-ZOSzfN($W)(da~l.lJ1zOSz{N(~'1)fiS(H~)l} ~3,L~+zHNZOSZHN
t''3.1.+zHN~(H~) zUdQ3W,IJ!'-I1I!S(H~)I~zOS~~OJBda+HN
X 'EN '!'INzIIS(H~)1rf'o'~ NrI
'S' 0~-i0-866l G9b8ZZZ0 ~a y The crosslinking reaction may imply the totality of the sulfonyl groups or a fraction of them. The crosslinking reagents may be applied by different techniques which are known to one skilled in the art. Conveniently, the processable thermoplastic or soluble material is shaped to the desired final form before crosslinking, e. g. membranes or hollow tubes and the material is brought in contact, by immersion or coating with a solution of the crosslinking reagent in a solvent which is non reactive towards the reactants. Appropriate solvents include but are not limited to polyhalocarbons, THF, the glymes, tertiary alkylamides including DMF, N methyl-pyrrolidone, tetraethyl urea and its cyclic analogs, N-alkyl-imidazoles, tetraalkyl sulfamides. The desired degree of crosslinking may be controlled by several factors such as time of contact, temperature or the concentration of the crosslinking reagent.
Alternatively, a latex of the processable material is intimately mixed with the reagent in solid form and the mixture is pressed or hot rolled, possibly in the presence of a non-solvent fluid such as an hydrocarbon. This technique is applicable in particular to thin membrane and results in high productivity though less homogeneous material is produced. It is understood that fillers such as powders, woven or non-woven fibers or filaments, can be added to the polymers before the crosslinking reaction as reinforcing agents.
If only a fraction of bridging bonds are required, the remaining -S02Y can be transformed into the ionic sulfonate form by alkaline hydrolysis.
Alternatively, the -S03M group or the non crosslinking imide group -S02NS02RFM can be obtained in the same conditions as for the crosslinks by ionogen reagents like respectively M+[{CH3)3Si0]- or M+[(CH3)3SiNS02RF]-; such examples are given for illustration but are not limitative. It may be advantageous to treat the membrane either sequentially by the crosslinking agent than by the non crosslinking ionogen reagents. Alternatively, the ionogen crosslinking agent and the non crosslinking ionogen are mixed together or codissolved in the solvent in predetermined proportions and react simultaneously.
The crosslinked material of the invention can be easily separated from the reactant products, which are either volatile like (CH3)3SiF or (CH3)3SiC1 or can be washed away in an appropriate solvent like water. Also, well known techniques from one skilled in the art like ion exchange or electrophoresis can be applied to exchange the cation M+ for the final application, (e.g. H+).
Claims (36)
1) Process for crosslinking sulfonated polymers, characterized in that at least some of the bonds linking the chains bear an ionic charge and involve, partially or in their totality, sulfonyl groups through interchain linkage of the following type:
P~SO2Y(M+)SO2~P' P~SO2(M+)Y-SO2Y-(M+)SO2~P' P~SO2(M+)Y-SO2QSO2Y-(M+)SO2~P' where:
P and P' represent polymer backbones Y represents:
- N (Nitrogen) CH, CQ where Q represents a monovalent, possibly fluorinated or perfluorinated alkyl, oxaalkyl, azaalkyl, aryl or arylalkyl or alkylaryl radical containing 2 to 20 carbon atoms, SO2R CCN, CF
Q represents a divalent, alkyl, oxaalkyl, azaalkyl, aryl or arylalkyl or alkylaryl radical containing 1 (inclusive) to 20 (inclusive) carbon atoms, possibly halogenated, in particular perfluorinated.
P~SO2Y(M+)SO2~P' P~SO2(M+)Y-SO2Y-(M+)SO2~P' P~SO2(M+)Y-SO2QSO2Y-(M+)SO2~P' where:
P and P' represent polymer backbones Y represents:
- N (Nitrogen) CH, CQ where Q represents a monovalent, possibly fluorinated or perfluorinated alkyl, oxaalkyl, azaalkyl, aryl or arylalkyl or alkylaryl radical containing 2 to 20 carbon atoms, SO2R CCN, CF
Q represents a divalent, alkyl, oxaalkyl, azaalkyl, aryl or arylalkyl or alkylaryl radical containing 1 (inclusive) to 20 (inclusive) carbon atoms, possibly halogenated, in particular perfluorinated.
2) Crosslinked sulfonated polymers, characterized in that at least some of the bonds linking the chains bear an ionic charge and involve, partially or in their totality, the sulfonyl groups through interchain linkage of the following type:
P~SO2Y(M+)SO2~P' P~SO2(M+)Y-SO2Y-(M+)SO2~P' P~SO2(M+)Y-SO2QSO2Y-(M+)SO2~P' where Y, P and P' are as defined in claim 1.
P~SO2Y(M+)SO2~P' P~SO2(M+)Y-SO2Y-(M+)SO2~P' P~SO2(M+)Y-SO2QSO2Y-(M+)SO2~P' where Y, P and P' are as defined in claim 1.
3) Process for crosslinking polymers according to claim 1, characterized in that the sulfonated groups are totally or partially in the form:
P~SO2L
where:
L = is a leaving group, like F, Cl, Br, an electrophilic heterocycle N-imidazolyl, N-triazolyl, R"SO3, R" being an organic radical, preferably halogenated, especially perfluorinated.
P~SO2L
where:
L = is a leaving group, like F, Cl, Br, an electrophilic heterocycle N-imidazolyl, N-triazolyl, R"SO3, R" being an organic radical, preferably halogenated, especially perfluorinated.
4) Process for crosslinking polymers according to claim 1, characterized in that the crosslinking agents are of the general formula:
(M+)A2Y
(M+)AYSO2YA(M+) (M+)AYSO2QYA(M+)
(M+)A2Y
(M+)AYSO2YA(M+) (M+)AYSO2QYA(M+)
5) Process for crosslinking polymers according to claim 1, characterized in that one of the following reactions is used to form the crosslinks:
P~SO2L + (M+)A2Y + LO2S~P' ~ P~SO2Y(M+)O2S~P' + 2LA
P~SO2L + (M+)AYSO2YA(M+) + LO2S~P' ~
P-SO2Y(M+)SO2Y(M+)SO2~P' + 2LA
P~SO2L + (M+)AYSO2QYA(M+) + LO2S~P' ~
P~SO2Y(M+)SO2QSO2Y(M+)SO2~P' + 2LA
P~SO2L + (M+)A2Y + LO2S~P' ~ P~SO2Y(M+)O2S~P' + 2LA
P~SO2L + (M+)AYSO2YA(M+) + LO2S~P' ~
P-SO2Y(M+)SO2Y(M+)SO2~P' + 2LA
P~SO2L + (M+)AYSO2QYA(M+) + LO2S~P' ~
P~SO2Y(M+)SO2QSO2Y(M+)SO2~P' + 2LA
6) Process for crosslinking polymers according to claim 3, characterized in that the sulfonated groups are totally or partially in the form:
P-SO2Y(M+)A
P-SO2Y(M+)A
7) Process for crosslinking polymers according to claim 4, characterized in that one of the following reactions is used to form the crosslinks:
P~SO2Y(M+)A + LSO2L + A(M+)Y~P' ~
P-SO2Y(M+)SO2Y(M+)SO2~P' + 2LA
P~SO2Y(M+)A + LSO2QSO2L + A(M+)Y~P' ~
P~SO2Y(M+)SO2QSO2Y(M+)SO2~P' + 2LA
P~SO2Y(M+)A + LSO2L + A(M+)Y~P' ~
P-SO2Y(M+)SO2Y(M+)SO2~P' + 2LA
P~SO2Y(M+)A + LSO2QSO2L + A(M+)Y~P' ~
P~SO2Y(M+)SO2QSO2Y(M+)SO2~P' + 2LA
8) Process for crosslinking polymers according to claims 3 and 4, characterized in that either M+ or A or both is a proton and the reaction is conducted in the presence of a tertiary or hindered organic base, an organometallic reagent, a metal amide.
9) Process for crosslinking polymers according to claim 4, characterized in that A is a trialkylsilyl group, especially trimethylsilyl.
10) Process according to claim 4, characterized in that A is a tertioalkyl group and the condensation reaction is conducted in the presence of a tertiary or hindered organic base.
11) Process for cross-linking polymers according to claim 8 characterized in that the tertiary base is triethylamine, di-isopropylamine, quinuclidine, 1,4-diazobicyclo[2,2,2] octane (DABCO); pyridines (for example pyridine, alkylpyridines, dialkylaminopyridines); imidazoles (for example N-alkylimidazoles, imidazo[1,1-a]pyridines, amidines (for example 1,5-diazabicyclo[4,3,0]non-5-ene (DBN), 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU); guanidines (for example tetramethyl guanidine, 1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine (HPP).
12) Process according to claim 3, characterized in that either A or M+ or both are solvated by dialkylethers or oligo-ethylene glycols or permethylated oligo-ethylendiamines (e.g. tetramethyl-ethylene diamine TMEDA).
13) Crosslinked polymers derived from at least one of the following monomers:
or or: or:
or: - X represents F, Cl or CF3 - n 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.
or or: or:
or: - X represents F, Cl or CF3 - n 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.
14) Crosslinked polymers according to claim 13, characterized in that L = F or Cl.
15) Crosslinked polymers according to claim 13, characterized in that n = O
included or 1.
included or 1.
16) Process according to claim 4, characterized in that the crosslinking agent is chosen between:
17) Process according to claim 6, characterized in that the crosslinking agent is chosen between:
18) Sulfonated polymers according to claim 2, characterized in that the uncrosslinked polymer containing the P~SO2L is processed into its final shape and crosslinked in a further step.
19) Sulfonated polymers according to claim 2, characterized in that the uncrosslinked polymer is mechanically mixed with the cross-linking agent and pressed and heated, preferably at temperatures ranging from 0 to 200°C.
20) Sulfonated polymers according to claim 2, characterized in that the uncrosslinked polymer is processed into its final shape and brought into contact with a solution of the crosslinking reagent in an inert solvent and reacted at a temperature ranging from -20 to 200°C.
21) Sulfonated polymers according to claim 2, characterized in that the crosslink density is controlled by the immersion time, the temperature and the concentration of the reagent.
22) Method for preparing thin membrane according to claim 11, characterized in that the suitable solvent is chosen among: lower aliphatic alcohols, acetone, methyl-ethylketone, cyclic ketones, cyclic ethers, the glymes, N-alkyl-pyrolidones, tetraalkylsulfamides, methylene chloride, chloroform, 1,2 dichloroethane, N-alkylimidazole, fluorinated hydrocarbons and mixtures thereof.
23) Method for preparing material according to claims 3 to 6, characterized in that ion exchange to the desired cation M+ is performed after polymerization.
24) Method according to claims 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.
25) Electrochemical cell characterized in that a membrane according to claims to 11, 13 to 19 is used as solid electrolyte.
26) Electrochemical cell according to claim 20, characterized in that it is a fuel cell, and/or a water electrolyser, a chlor-alkali cell, an electrochemical acid or salt recovery cell.
27) Electrochemical cell according to claim 20, characterized in that at least one electrode is in contact with the membrane.
28) Electrochemical cell according to claim 22, characterized in that at least one electrode containing a conducting additive, optionally a catalyst, optionally a pore forming agent and the un-crosslinked polymer of claim 2 is coated on the pre-crosslinked electrolyte membrane, then crosslinked.
29) Electrochemical cell according to claim 23, characterized in that at least one electrode containing a conductive additive, optionally a catalyst, and optionally a pore forming agent and the monomers of claims 1 to 6 are coated on, or co-extruded with, the un-crosslinked electrolyte membrane, then crosslinked.
30) 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 either an hydrogen, methanol, dimethoxymethane, trimethoxymethane, trioxane or ammonia oxidation catalyst.
31) Fuel cell according to claim 26, characterized in that the electrodes are applied onto the membrane using the process or either claims 23 or 24.
32) Material according to claims 1 to 11, characterized in that it is used for chlor-alkali electrolysis.
33) Material according to claims 1 to 11 characterized in that it is used as a separator in the electrochemical preparation or organic or inorganic substances.
34) Material according to claims 1 to 11 and 18, characterized in that it is used as a separator between an aqueous phase and an organic phase.
35) Material according to claims 1 to 11 and 12, characterized in that the M+
ions associated with the non-nucelophilic anionic centers of the backbone confer catalytic properties.
ions associated with the non-nucelophilic anionic centers of the backbone confer catalytic properties.
36) Material according to claims 1 to 11 and 20, characterized in that it is a catalyst for Diels & Alder additions, Friedel & Craft reactions, aldol condensations, cationic polymerization, esterifications, acetal formation.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2228467 CA2228467A1 (en) | 1998-01-30 | 1998-01-30 | New techniques and processes for crosslinking ion exchange membranes and their applications |
| JP53874999A JP4477149B2 (en) | 1998-01-30 | 1999-01-29 | Crosslinked sulfonated polymer and process for its production |
| PCT/CA1999/000078 WO1999038897A1 (en) | 1998-01-30 | 1999-01-29 | Cross-linked sulphonated polymers and method for preparing same |
| DE69940033T DE69940033D1 (en) | 1998-01-30 | 1999-01-29 | Process for the preparation of crosslinked sulfonated polymers |
| DE69916715T DE69916715T2 (en) | 1998-01-30 | 1999-01-29 | NETWORKED SULPHONATED POLYMERS AND METHOD FOR THE PRODUCTION THEREOF |
| CA2283668A CA2283668C (en) | 1998-01-30 | 1999-01-29 | Cross-linked sulphonated polymers and method for preparing same |
| EP03024852A EP1400539B1 (en) | 1998-01-30 | 1999-01-29 | Method for preparing crosslinked sulfonated polymers |
| EP99902478A EP0973809B1 (en) | 1998-01-30 | 1999-01-29 | Cross-linked sulphonated polymers and method for preparing same |
| US09/390,648 US6670424B1 (en) | 1998-01-30 | 1999-09-07 | Ross-linked sulphonated polymers and their preparation process |
| US09/906,702 US20020002240A1 (en) | 1998-01-30 | 2001-07-18 | Cross-linked sulphonated polymers and method for preparing same |
| US10/094,047 US6649703B2 (en) | 1998-01-30 | 2002-03-08 | Cross-linked sulphonated polymers and their preparation process |
| US10/813,692 US7034082B2 (en) | 1998-01-30 | 2003-05-14 | Cross-linked sulphonated polymers and their preparation process |
| US11/380,133 US7674560B2 (en) | 1998-01-30 | 2006-04-25 | Cross-linked sulphonated polymers and their preparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2228467 CA2228467A1 (en) | 1998-01-30 | 1998-01-30 | New techniques and processes for crosslinking ion exchange membranes and their applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2228467A1 true CA2228467A1 (en) | 1999-07-30 |
Family
ID=29409201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2228467 Abandoned CA2228467A1 (en) | 1998-01-30 | 1998-01-30 | New techniques and processes for crosslinking ion exchange membranes and their applications |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2228467A1 (en) |
-
1998
- 1998-01-30 CA CA 2228467 patent/CA2228467A1/en not_active Abandoned
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