CA2236197A1 - 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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- CA2236197A1 CA2236197A1 CA 2236197 CA2236197A CA2236197A1 CA 2236197 A1 CA2236197 A1 CA 2236197A1 CA 2236197 CA2236197 CA 2236197 CA 2236197 A CA2236197 A CA 2236197A CA 2236197 A1 CA2236197 A1 CA 2236197A1
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- C08J5/2218—Synthetic macromolecular compounds
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Abstract
Crosslinking sulfonated polymers through sulfonimide, bis(sulfonyhmethane) or tris(sulfonylmethane) chains containing an ionic charge.
Description
New '1'eclmiyues uud 1'ruc:esses tur Crussliulciul; lua Lxhange IVIeuWraues and their Ahhlicaliuus lnvention by Chrislophe Nlichot and Michel Armand Previuus Art:
Owing to their chemical inertness, fluorinated or perfluorinated ion exchange membranes have been selected for the chlor-alkali process and fur fuel cells consuming either hydrogen or' methanol. The materials presently available under the commercial names Nafion " ) Flemion~) Down or materials developed by Ballard lnc. (WOy7/253Gy) arc copolymers of tetrafluoroethyleuc ('1'I~G) and of perfluorovinylethers or trifluorovinylstryrene. The active monomers bear chemical functionalities which are the precursors of ionic groups of the sulfonate or carboxylate type.
'These precursors are for'instance F2C=CF-O CF2- i F-O CF2-CF2-SOZF
X n or:
or F2C=CF- O CF2 i F-O (CF2~C02CH3 X n F2C=CF --« J J-S02F
sulfonated polyaromatic insides or ether sulfones have also been considered as candidates:
fo-o-c~-o-o-~~
sqv where:
- X represents F) CI or CF3 - 0 <_ n <_ 10 -p=lor2 Once obtained the copolymer containing the precursors is processed into sheets then transformed into the ionic form by hydrolysis (-S02F ~ -S03-M+; -C02CH3 ~ -COZ-M+).
where:
- M+ represents a cation, with for example: H+, Li+) Na+, K+) 1/2Mg2+, 1/2Ca2+, 1/2Ba2+ and other alkaline earth metals ions) 1/2Zn2+, 1/2Cu2+ and other transition metals ions, 1/3A13+) 1/3Fe3+) 1/3Sc-~+) 1/3Y3+, l/3La3+ and other rare earth metals ions) or an organic cation of the opium type, oxoniun, ammonium or pyridinium, guanidinium, amidinium) sulfonium, phosphoniunl, non sunsliluled) partially or totally substituted by organic radicals, organometallic canons, like metalloceniunls, arene-ferrocenium) alkylsilyl, alkylgermanyl, alkyltin...
Such materials have however several important drawbacks which are suuun~u~ized below:
1 ) the copolymers in their ionic form are unlraclable, yet are not dimensionally stable and swell appreciably in water and polar solvents. Only when heated al high temperature in supercritical water-lower alcools nlixlures they eau form inverse nlicelles which, upon evaporation, leave the cnalerials as films. However this recast marerial is in a form lacking mechanichal cohesiveness.
Owing to their chemical inertness, fluorinated or perfluorinated ion exchange membranes have been selected for the chlor-alkali process and fur fuel cells consuming either hydrogen or' methanol. The materials presently available under the commercial names Nafion " ) Flemion~) Down or materials developed by Ballard lnc. (WOy7/253Gy) arc copolymers of tetrafluoroethyleuc ('1'I~G) and of perfluorovinylethers or trifluorovinylstryrene. The active monomers bear chemical functionalities which are the precursors of ionic groups of the sulfonate or carboxylate type.
'These precursors are for'instance F2C=CF-O CF2- i F-O CF2-CF2-SOZF
X n or:
or F2C=CF- O CF2 i F-O (CF2~C02CH3 X n F2C=CF --« J J-S02F
sulfonated polyaromatic insides or ether sulfones have also been considered as candidates:
fo-o-c~-o-o-~~
sqv where:
- X represents F) CI or CF3 - 0 <_ n <_ 10 -p=lor2 Once obtained the copolymer containing the precursors is processed into sheets then transformed into the ionic form by hydrolysis (-S02F ~ -S03-M+; -C02CH3 ~ -COZ-M+).
where:
- M+ represents a cation, with for example: H+, Li+) Na+, K+) 1/2Mg2+, 1/2Ca2+, 1/2Ba2+ and other alkaline earth metals ions) 1/2Zn2+, 1/2Cu2+ and other transition metals ions, 1/3A13+) 1/3Fe3+) 1/3Sc-~+) 1/3Y3+, l/3La3+ and other rare earth metals ions) or an organic cation of the opium type, oxoniun, ammonium or pyridinium, guanidinium, amidinium) sulfonium, phosphoniunl, non sunsliluled) partially or totally substituted by organic radicals, organometallic canons, like metalloceniunls, arene-ferrocenium) alkylsilyl, alkylgermanyl, alkyltin...
Such materials have however several important drawbacks which are suuun~u~ized below:
1 ) the copolymers in their ionic form are unlraclable, yet are not dimensionally stable and swell appreciably in water and polar solvents. Only when heated al high temperature in supercritical water-lower alcools nlixlures they eau form inverse nlicelles which, upon evaporation, leave the cnalerials as films. However this recast marerial is in a form lacking mechanichal cohesiveness.
2) handling of TFE is hazardous, as its polymerization is under pressure and my lead to runaway reactions) especially in the presence of oxygen; due to the difference in boiling points',bf the two monomers, it is difficult.to obtain of a statistical pulymer 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.
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.
4) the permeation of methanol and of oxygen through the membrane is high, as the perfluorocarbon part of the polymer allows facile diffusion of molecular species, resulting in crossover chemical reaction and a loss of faladaic efficiency, in particular for direct nletlnulol fuel cells (DMFC's).
Non fluorinated systems like sulfonaled polyimides or polyethcr 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 from the person skilled in the 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 eau be achieved after the polymer has been shaped while in the processable non ionic precursor form. The invention also relates to the use of the crosslinked material in the membrane form for applications including fuel cells, wafer electrolysis, chlor-alkali process, electrosynthesis) v~ialer treatment and ozone production.
The creation of stable crosslinks is achieved though the reaction of two -S02Y
from adjacent chains to form the sulfoninlide, bis(sulfonylmelhane) or iris sulfonylmelhane derivatives, schematized as:
SOIL +LS02 A2Y_(M+) t S02 Z~-O2 M+
+ 2 LA
or L(M+)-YS02Y-(M+)L
i M+ M+
+ 2 LA
or:
S02L + L02S
A(M+)-YS02QS02Y-(M+)A
o i o S02 YS02QSOzY-S02 M+ M+
+ 2 LA
Where M has the above signification and Y represents:
- N (Nitrogen) - CH) CCN, CR where R represents au alkyl or alkylene with 1 to 20 carbons) halogenated or not) possibly bearing aza or oxa subtituents, or '1' or an alkyl- or an alkylene- sulfonyl group, with 1 to 20 carbons) halogenated or not) possibly bearing aza or oxa subtituents, including TS 02.
A = M or Si(R')3) Ge(R')3, Sn(R')3, (R' = alkyl from 1 to 18 carbon atoms) Q = a divalent) alkyl) ~ oxaalkyl, azaalkyl) aryl or arylalkyl or alkylaryl radical containning 1 (inclusive) to 20 (inclusive) carbon atoms, possibly halogenated, in p~u-ticular perfluorinated and optionally possibly including aza- or uxa- sublilucnls. Wl~cu lherc is no carbon atom, the compound is a sulfamide ur a sulfune.
The M+ species may themselves be solvated or complexed form to increase their solubility or reactivity.
For example, protons can be complexed by a strong nucleuphilic tertiary base like trielhylamine (1'EA)) dimethylaminopyridine (DMAY), 1,4-diazabicyclo[2.2.2]octane or as nascent form in the terliobulyl radical disproportionaling readily into H and CI-12=C(CI-I3)3; metallic ions are solvated ~y dialkylelhers of oligo-ethylene glycols, or permelhylaled oligo-elhylendiamines (e.g.
letramelhylelhylene-diamine TMEDA). Similarly, the A2Y-(M+) compound can be formed in situ in the presence of stong bases like 0 organometallics reacting on labile protons attached to the Y radical.
Suitable reagents include organo-lithium, -magnesium or -aluminium compounds compounds, which also serve as a source of'carbon for Y = CR, alkali metal amides as a source of nitrogen fur Y = N, dialkyl amides like LDA (lithium diisopropylanlide).
An advantage of the technique and materials of the invention is that the crosslinking agent creates
Non fluorinated systems like sulfonaled polyimides or polyethcr 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 from the person skilled in the 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 eau be achieved after the polymer has been shaped while in the processable non ionic precursor form. The invention also relates to the use of the crosslinked material in the membrane form for applications including fuel cells, wafer electrolysis, chlor-alkali process, electrosynthesis) v~ialer treatment and ozone production.
The creation of stable crosslinks is achieved though the reaction of two -S02Y
from adjacent chains to form the sulfoninlide, bis(sulfonylmelhane) or iris sulfonylmelhane derivatives, schematized as:
SOIL +LS02 A2Y_(M+) t S02 Z~-O2 M+
+ 2 LA
or L(M+)-YS02Y-(M+)L
i M+ M+
+ 2 LA
or:
S02L + L02S
A(M+)-YS02QS02Y-(M+)A
o i o S02 YS02QSOzY-S02 M+ M+
+ 2 LA
Where M has the above signification and Y represents:
- N (Nitrogen) - CH) CCN, CR where R represents au alkyl or alkylene with 1 to 20 carbons) halogenated or not) possibly bearing aza or oxa subtituents, or '1' or an alkyl- or an alkylene- sulfonyl group, with 1 to 20 carbons) halogenated or not) possibly bearing aza or oxa subtituents, including TS 02.
A = M or Si(R')3) Ge(R')3, Sn(R')3, (R' = alkyl from 1 to 18 carbon atoms) Q = a divalent) alkyl) ~ oxaalkyl, azaalkyl) aryl or arylalkyl or alkylaryl radical containning 1 (inclusive) to 20 (inclusive) carbon atoms, possibly halogenated, in p~u-ticular perfluorinated and optionally possibly including aza- or uxa- sublilucnls. Wl~cu lherc is no carbon atom, the compound is a sulfamide ur a sulfune.
The M+ species may themselves be solvated or complexed form to increase their solubility or reactivity.
For example, protons can be complexed by a strong nucleuphilic tertiary base like trielhylamine (1'EA)) dimethylaminopyridine (DMAY), 1,4-diazabicyclo[2.2.2]octane or as nascent form in the terliobulyl radical disproportionaling readily into H and CI-12=C(CI-I3)3; metallic ions are solvated ~y dialkylelhers of oligo-ethylene glycols, or permelhylaled oligo-elhylendiamines (e.g.
letramelhylelhylene-diamine TMEDA). Similarly, the A2Y-(M+) compound can be formed in situ in the presence of stong bases like 0 organometallics reacting on labile protons attached to the Y radical.
Suitable reagents include organo-lithium, -magnesium or -aluminium compounds compounds, which also serve as a source of'carbon for Y = CR, alkali metal amides as a source of nitrogen fur Y = N, dialkyl amides like LDA (lithium diisopropylanlide).
An advantage of the technique and materials of the invention is that the crosslinking agent creates
5 ionophoretic, i.e. charged species, the negatively charges moieties being auached to the polymer and used as bridges between chains. It is known that the sulfonylinlide groups and di or trisulfonylmethane groups are strong electrolytes in most media and thus the crosslinking reaction, in addition to improving the mechanichal properties, has no detrimental effect on the conductivity and often results in its enhancement.
The compounds whose formulae are given below are examples of suitable ionogen crosslinking agents !0 and are given to illustrate the principle of the invention but we not limiting its the scope:
Li~N C3AI4 [(CI-13)3Si]2NLi, Na) K
NH3 + 3DABC0 CF3S02C[(CH3)3Si][Li(TMEDA)]2(Cl-I3)3CN1-I2 + 3TEA
NH2S02NH2 + 4TEA ( [(CH~)~Si](Li)N ) 2S02 [(TMEDA)(Nlg)N]2S02 CH3Li (CH~)~A1 NH2Li) Na, K
{ [Si(CH3)~](Li)NS02 { (Li)[Si(CH3)3]NSOZCF2 [(Li)Si(CH3)3NS02CF2]2 ) 2CFZ ) 2CF2 ( (Li)[Si(CH~)~]NS02CF2CFz }20 Alternatively, the cross linking reaction can take place with when the Y group is already on the polymer precursor, as for a substituted anode; the general scheme in this case is schematized as:
p p M+ M+
+ 2 LA LSOZL
pt O
M+ M+
+ 2 LA
ur:
O O
M+ M+
o i o M+ M+
+ 2 LA
The compounds whose formulae we given below are examples of suitable ionogen crosslinking agents and are given to illustrate the principle of the invention buWu~e non linuting:
S02C12 + 3DABC0 S02(inudazole)2 ~rsO2Cr2~2 +
3'1'EA
(IS02CP2CI=2)20 + 3DA13C0 The crosslinking reaction lay imply the totality of the sulfonyl groups or a fraction of tHel. The crosslinking reagents may be applied by different leclniiques which are known to the man skilled is 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 in brought in contact) by immersion or coating with a solution of the crosslinking reagent in a solvents which promotes the coupling reaction but is not itself effected by tl~e reactants. Appropriate solvents include but are not limited to) polyHalocarbons) 'fl-iF, the glyles) tertiary alkylawides including DMP) N-lethyl-pyrrolidone, tetramethyl-urea and its cyclic analogs, N-alkylimidazoles, tetraalkyl sulfalides. The desired degree of crosslinkinbg may be controlled by several factors, like tile of contact) temperature or the concentration of the crosslinking reagent.
Alternatively, a latex of the processuble material is iutin~ately mixed with the reagent in the solid form and the mixture is pressed or Hot rolled, possibly is the presence of a non-solvent fluids like au hydrocarbon.
This technique is applicable in particular to thin membrane and results in high productivity) though possibly less homogeneous material is pruduced. ll is understood lhul fillers, as powders, woven ur non-woven fibers or filanlenls) eau be added lu the pulynlers before the crosslinking reaction as reinforcing agents.
if only a fraction of bridging bonds ure rcyuired, the remaining -SOZY eau be transformed info the ionic sulfonale furor by alkaline hydrulysis. Alternatively, in a preferred CIllbOdlillelll, lllc -SO~M group or the non crosslinking inside group -S02NS02Rt:M can be obtained is file same conditions as for the crosslinks by ionogenic reagents like respectively M[(Cl-f3)3SiOJ or Ivl[(CH~)3SiNS02Rr]; such compounds are examples given fur illustration but are not linliling the scope of this methode. It may be advantageous to treat the meu~braue eilller seyuenlially by the crosslinking agent then by the non crosslinking ionogenic reagents. Alternatively, the ionogenic crosslinking agent and the non-crossliukiug ionogelmixed together or co-dissolved in the solvent in predelernlined proportions and react simultaneously.
The crosslinked material of the invenliun eau be easily separated from the reaction pruducls, which are either volatile like (CH3)3SiF or (CH3)3SiC1 or eau be washed away is au appropriate solvent like wafer or an organic fluid. Also, well known lechniyues front the Luau skilled in the art like ion exchange or electrophoresis eau be applied to exchange the calion Nl+ obtained in the crosslinking reaction and/or front the non crosslinking ionogen reagents wish llle desired M'+ for the final application) (e.g. H+).
The compounds whose formulae are given below are examples of suitable ionogen crosslinking agents !0 and are given to illustrate the principle of the invention but we not limiting its the scope:
Li~N C3AI4 [(CI-13)3Si]2NLi, Na) K
NH3 + 3DABC0 CF3S02C[(CH3)3Si][Li(TMEDA)]2(Cl-I3)3CN1-I2 + 3TEA
NH2S02NH2 + 4TEA ( [(CH~)~Si](Li)N ) 2S02 [(TMEDA)(Nlg)N]2S02 CH3Li (CH~)~A1 NH2Li) Na, K
{ [Si(CH3)~](Li)NS02 { (Li)[Si(CH3)3]NSOZCF2 [(Li)Si(CH3)3NS02CF2]2 ) 2CFZ ) 2CF2 ( (Li)[Si(CH~)~]NS02CF2CFz }20 Alternatively, the cross linking reaction can take place with when the Y group is already on the polymer precursor, as for a substituted anode; the general scheme in this case is schematized as:
p p M+ M+
+ 2 LA LSOZL
pt O
M+ M+
+ 2 LA
ur:
O O
M+ M+
o i o M+ M+
+ 2 LA
The compounds whose formulae we given below are examples of suitable ionogen crosslinking agents and are given to illustrate the principle of the invention buWu~e non linuting:
S02C12 + 3DABC0 S02(inudazole)2 ~rsO2Cr2~2 +
3'1'EA
(IS02CP2CI=2)20 + 3DA13C0 The crosslinking reaction lay imply the totality of the sulfonyl groups or a fraction of tHel. The crosslinking reagents may be applied by different leclniiques which are known to the man skilled is 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 in brought in contact) by immersion or coating with a solution of the crosslinking reagent in a solvents which promotes the coupling reaction but is not itself effected by tl~e reactants. Appropriate solvents include but are not limited to) polyHalocarbons) 'fl-iF, the glyles) tertiary alkylawides including DMP) N-lethyl-pyrrolidone, tetramethyl-urea and its cyclic analogs, N-alkylimidazoles, tetraalkyl sulfalides. The desired degree of crosslinkinbg may be controlled by several factors, like tile of contact) temperature or the concentration of the crosslinking reagent.
Alternatively, a latex of the processuble material is iutin~ately mixed with the reagent in the solid form and the mixture is pressed or Hot rolled, possibly is the presence of a non-solvent fluids like au hydrocarbon.
This technique is applicable in particular to thin membrane and results in high productivity) though possibly less homogeneous material is pruduced. ll is understood lhul fillers, as powders, woven ur non-woven fibers or filanlenls) eau be added lu the pulynlers before the crosslinking reaction as reinforcing agents.
if only a fraction of bridging bonds ure rcyuired, the remaining -SOZY eau be transformed info the ionic sulfonale furor by alkaline hydrulysis. Alternatively, in a preferred CIllbOdlillelll, lllc -SO~M group or the non crosslinking inside group -S02NS02Rt:M can be obtained is file same conditions as for the crosslinks by ionogenic reagents like respectively M[(Cl-f3)3SiOJ or Ivl[(CH~)3SiNS02Rr]; such compounds are examples given fur illustration but are not linliling the scope of this methode. It may be advantageous to treat the meu~braue eilller seyuenlially by the crosslinking agent then by the non crosslinking ionogenic reagents. Alternatively, the ionogenic crosslinking agent and the non-crossliukiug ionogelmixed together or co-dissolved in the solvent in predelernlined proportions and react simultaneously.
The crosslinked material of the invenliun eau be easily separated from the reaction pruducls, which are either volatile like (CH3)3SiF or (CH3)3SiC1 or eau be washed away is au appropriate solvent like wafer or an organic fluid. Also, well known lechniyues front the Luau skilled in the art like ion exchange or electrophoresis eau be applied to exchange the calion Nl+ obtained in the crosslinking reaction and/or front the non crosslinking ionogen reagents wish llle desired M'+ for the final application) (e.g. H+).
-6-
Claims (40)
1) process for crosslinking sulfonated polymers, characterized in that at least some of the bonds linking the chains bears au 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:
P and P' represents two different strands of the polymer backbone.
Y represents:
- N (Nitrogen) - CH, CCN, CR where R represents an alkyl or alkylene with 1 to 20 carbons, halogenated or not, possibly bearing aza or oxa subtituents, or T or an alkyl- or an alkylene-sulfonyl group, with 1 to 20 carbons, halogenated or not, possibly bearing aza or oxa subtituents, including TSO2.
Q represents a divalent, alkyl, oxaalkyl, azaalkyl, aryl or arylalkyl or alkylalyl radical containing 1 (inclusive) to 20 (inclusive) carbon atoms, possibly halogenated, is particular perfluorinated and optionally possibly including aza- or oxa- subtituents. When there is no carbon atom, the compound is a sulfamide or a sulfone
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' represents two different strands of the polymer backbone.
Y represents:
- N (Nitrogen) - CH, CCN, CR where R represents an alkyl or alkylene with 1 to 20 carbons, halogenated or not, possibly bearing aza or oxa subtituents, or T or an alkyl- or an alkylene-sulfonyl group, with 1 to 20 carbons, halogenated or not, possibly bearing aza or oxa subtituents, including TSO2.
Q represents a divalent, alkyl, oxaalkyl, azaalkyl, aryl or arylalkyl or alkylalyl radical containing 1 (inclusive) to 20 (inclusive) carbon atoms, possibly halogenated, is particular perfluorinated and optionally possibly including aza- or oxa- subtituents. When there is no carbon atom, the compound is a sulfamide or a sulfone
2) crosslinked sulfamide polymers, characterized in that at least some of the bonds linking the chains bears 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+)Z-SO2-Z-(M+)SO2~P
P~SO2(M+)Z-SO2QSO2Z-(M+)SO2-P
P~SO2Y-(M+)SO2~P
P~SO2(M+)Z-SO2-Z-(M+)SO2~P
P~SO2(M+)Z-SO2QSO2Z-(M+)SO2-P
3) process for crosslinking polymers according to claim 2 characterized in that the sulfonated groups are totally or partially under the form :
P~SO2L
where:
L = is a leaving group, like F, Cl, Br, au electrophilic heterocycle N-imidazolyl, N-triazolyl, R"SO3, R" being au organic radical, preferably halogenated, especially fluorinated.
P~SO2L
where:
L = is a leaving group, like F, Cl, Br, au electrophilic heterocycle N-imidazolyl, N-triazolyl, R"SO3, R" being au organic radical, preferably halogenated, especially fluorinated.
4) process for crosslinking polymers according to claim 2 characterized in that the crosslinking agents are of the general formula:
(M+)A2Z
(M+)AZSO2ZA(M+) (M+)AZSO2QZA(M+)
(M+)A2Z
(M+)AZSO2ZA(M+) (M+)AZSO2QZA(M+)
5) process for crosslinking polymers according to claim 2 characterized in that one of the following reactions is used to form the crosslinks:
P~SO2L+(M+)A2Y + LO2S~P'~ P~SO2Z(M+)O2S~P'+2LA
P~SO2L+(M+)AYSO2ZA(M+) + LO2S~P' ~
P~SO2Z(M+)SO2Y(M+)SO2~P' + 2LA
P~SO2L + (NI+)AYSO2QZA(M+) + LO2S~P'~
P~SO2Y(M+)SO2QSO2Y(M+)SO2~P'+2LA
P~SO2L+(M+)A2Y + LO2S~P'~ P~SO2Z(M+)O2S~P'+2LA
P~SO2L+(M+)AYSO2ZA(M+) + LO2S~P' ~
P~SO2Z(M+)SO2Y(M+)SO2~P' + 2LA
P~SO2L + (NI+)AYSO2QZA(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 under 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~SO2Z(M+)SO2Z(M+)SO2~P' + 2LA
P~SO2Y(M+)A + LSO2QSO2L + A(M+)Y~P' ~
P~SO2Z(M+)SO2QSO2Z(M+)SO2~P' + 2LA
P~SO2Y(M+)A + LSO2L + A(M+)Y-P' ~
P~SO2Z(M+)SO2Z(M+)SO2~P' + 2LA
P~SO2Y(M+)A + LSO2QSO2L + A(M+)Y~P' ~
P~SO2Z(M+)SO2QSO2Z(M+)SO2~P' + 2LA
8) process for crosslinking polymers according to claim 3 and 4 characterized in that either M+ or A or both is a proton and the reaction is conducted in 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 tertialy or hindered organic base.
11) process for crosslinking polymers according to claim 8 and 10 characterized in that the tertiary base is triethylamine) di-isopropylamine, quinuclidine), 1,4-diazobicyclo[2,2,2]octane (DABCO); a pyridine (for example pyridine, alkylpryidines, dialkylaminopyridine); an imidazole (for example N-alkylimidazoles, imidazo[1,1-a]pyridine); as amidine (for example 1,5-diazabicyclo[4,3,0]non-5-ene (DBN), 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU); a guanidine (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 enter A or M+ or both are solvated by dialkylethers or oligo-ethylene glycols or permethylaled oligo-ethylendiamines (ex tetramethyl-ethylene diamine TMEDA).
13) crosslinked polymers derived from at least one of the following monomers:
where:
- X represents F, Cl or CF3 - a 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.
where:
- X represents F, Cl or CF3 - a 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 is that L = F or Cl.
15) crosslinked polymers according to claim 13 characterized in that n = 0 (included) or 1.
16) process according to claim 4 characterized in that the crosslinking agent are chosen between:
Li3N C3AI4 [(CH3)3Si]2NLi,Na, K
NH3 + 3DABCO CF3SO2C[(CH3)3Si][Li(TMEDA)]2 (CH3)3CNH2 + 3TEA
NH2SO2NH2 + 4TEA {[(CH3)3Si](Li)N]2SO2 [(TMEDA)(Mg)N]2SO2 CH3Li (CH3)3Al NH2Li, Na, K
{[Si(CH3)3](Li)NSO2]2CF ((Li)[Si(CH3)3]NSO2CF2)2CF2 [(Li)Si(CH3)3NSO2CF2]2 {(Li)[Si(CH3)3]NSO2CF2CF2}2O
Li3N C3AI4 [(CH3)3Si]2NLi,Na, K
NH3 + 3DABCO CF3SO2C[(CH3)3Si][Li(TMEDA)]2 (CH3)3CNH2 + 3TEA
NH2SO2NH2 + 4TEA {[(CH3)3Si](Li)N]2SO2 [(TMEDA)(Mg)N]2SO2 CH3Li (CH3)3Al NH2Li, Na, K
{[Si(CH3)3](Li)NSO2]2CF ((Li)[Si(CH3)3]NSO2CF2)2CF2 [(Li)Si(CH3)3NSO2CF2]2 {(Li)[Si(CH3)3]NSO2CF2CF2}2O
17) process according to claim 6 characterized in that the crosslinking agent are chosen between:
SO2Cl2 + 3DABCO SO2(imidazole)2 [FSO2CF2]2 + 3TEA
(FSO2CF2CF2)2O + 3DABCO
SO2Cl2 + 3DABCO SO2(imidazole)2 [FSO2CF2]2 + 3TEA
(FSO2CF2CF2)2O + 3DABCO
18) sulfonated polymers according to claims 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 claims 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 claims 2 characterized in that the uncrosslinked polymer is processed into its final shape and brought in contact with a solution of the crosslinking reagent in an inert solvent and reacted at temperatures ranging from -60 to 200°C.
21) sulfonate polymers according to claims 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 a membrane according to claim 20 characterized in that the suitable solvent is chosen among: lower aliphatic alcohols, polyhalocarbons, THF, the glymes, tertiary alkylamides including DMF, N-methyl-pyrrolidone, tetramethyl-urea and its cyclic analogs, N-alkylimidazoles, tetraalkyl sulfamides and mixtures thereof.
23) sulfonated polymers according to claims 2 characterized in that the uncrosslinked polymer is is processed into its final shape and brought in contact with the crosslinking reagent and a non-crosslinking ion-generating reagent to form ~SO3-(M+), or -[SO2YSO2R]-(M+) end groups, R"' being an organic radical, preferably halogenated, especially perfluorinated.
24) sulfonated polymers according to claims 23 characterized in that the uncrosslinked polymer is is processed info its final shape and brought in contact sequentially wills the crosslinking reagent and the non-crosslinking ion-generating reagent.
25) sulfonated polymers according to claims 23 characterized is that the uncrosslinked polymer is is processed info its final shape and brought in contact simultaneously wish the crosslinking reagent and the non-crosslinking ion-generating reagent, the crosslink density being controlled by the immersion time, the temperature and the concentration of the reagents.
26) sulfonated polymers according to claims 23 characterized in that the non-crosslinking ion-generating reagent, is (CH3)3SiO-(M+) or [(CH3)3SiNSO2CF3]-(M+).
27) Method for preparing material according to claims 2 to 26 characterized in that ion exchange to the desired cation M+ is performed offer polymerization.
28) Material according to claim 2 to 26 characterized in that inorganic or organic filler particles, including fibers, filaments, woven or non woven cloth , are included in the polymers while in the processable form.
29) electrochemical cell characterized in that a membrane according to claims 1 to 28 is used as solid electrolyte.
30) electrochemical cell according to claim 29 characterized in that it is a fuel cell, an/or a water electrolyser, a chlor-alkali cell, an electrochemical acid or salt recovery cell, an ozone production cell.
31) electrochemical cell according to claim 29 characterized in that at least one electrode is in contact with the membrane.
32) electrochemical cell according to claims 30 characterized in that at least one electrode containing a conductive additive, optionally a catalyst, optionally a pore forming agent and the un-crosslinked sulfonated polymer is coated on the pre-crosslinked electrolyte membrane, then crosslinked.
33) 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, is coated on, or co-extruded with, the un-crosslinked electrolyte membrane then the assembly crosslinked.
34) electrochemical cell according to claim 30 characterized in that it forms the element of a fuel cell where M+ is an hydrated proton and the positive electrode contains au oxygen reduction catalyst an the negative electrode either an hydrogen, methanol, dimethoxymethane, trimethoxymethane, trioxane or ammonia oxidation catalyst.
35) fuel cell according to claim 34 characterized in that the electrodes are applied onto the membrane using the process or either claims 32 or 34
36) Material according to claims 1 to 11 characterized in that it is used for chlor-alkali electrolysis.
37) Material according to claim 29 characterized in that it is used as a separator in the electrochemical preparation of organic or inorganic substances.
38) Material according to claims 29 characterized in that it is used a separator between an an aqueous phase and an organic phase.
39) Material according to claims 1 to 11 and 12 characterized in that the M+
ions associated with the non-nucleophilic anionic centers of the backbone confer catalytic properties.
ions associated with the non-nucleophilic anionic centers of the backbone confer catalytic properties.
40) 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 2236197 CA2236197A1 (en) | 1998-04-28 | 1998-04-28 | New techniques and processes for crosslinking ion exchange membranes and their applications |
| EP03024852A EP1400539B1 (en) | 1998-01-30 | 1999-01-29 | Method for preparing crosslinked sulfonated polymers |
| DE69916715T DE69916715T2 (en) | 1998-01-30 | 1999-01-29 | NETWORKED SULPHONATED POLYMERS AND METHOD FOR THE PRODUCTION THEREOF |
| JP53874999A JP4477149B2 (en) | 1998-01-30 | 1999-01-29 | Crosslinked sulfonated polymer and process for its production |
| EP99902478A EP0973809B1 (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 |
| CA2283668A CA2283668C (en) | 1998-01-30 | 1999-01-29 | Cross-linked sulphonated polymers and method for preparing same |
| PCT/CA1999/000078 WO1999038897A1 (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 2236197 CA2236197A1 (en) | 1998-04-28 | 1998-04-28 | New techniques and processes for crosslinking ion exchange membranes and their applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2236197A1 true CA2236197A1 (en) | 1999-10-28 |
Family
ID=29275618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2236197 Abandoned CA2236197A1 (en) | 1998-01-30 | 1998-04-28 | New techniques and processes for crosslinking ion exchange membranes and their applications |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2236197A1 (en) |
-
1998
- 1998-04-28 CA CA 2236197 patent/CA2236197A1/en not_active Abandoned
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