CA2283132C - Crosslinkable bi-sulphonyl derivatives and their uses for preparing ion-exchanging membranes - Google Patents

Abstract

The invention concerns novel ion-exchanging membranes, the method for preparing them and their uses. The membranes are made up of a polymer obtained from a monomer or a bifunctional mixture of monomers of general formula [T-SO¿2?-Y-SO¿2?T']?-¿ M-?+¿. Moreover said polymers are useful in electrochemical cells, in a chlorine-sodium electrolysis process, as separator in an electrochemical preparation of organic and inorganic compounds, as separator between an aqueous phase and an organic phase, or as catalyst for Diels-Alder additions, Friedel-Craft reactions, aldol condensations, cationic polymerisation, and acetal formation.

Description

WO 99/3884

2 PCT / CA99 / 00083 TITLE
POLYMERIZABLE BIS-SULFONYL DERIVATIVES AND THEIR USE IN PREPARATION
FROM MEM-BRANES EXCHANGES OF IONS

FIELD OF THE INVENTION

The present invention relates to ion exchange resins of the type cationic form, in particular in the form of membranes, optionally perfluorinated, useful in particular in electrochemical applications like batteries to fuels, chlorine-soda processes, electrodialysis, ozone production, sensors etc, or any another application related to the dissociation of the anionic centers fixed on the membrane, such than heterogeneous catalysis in organic chemistry.

PRIOR ART

Because of their chemical inertness, ion exchange membranes partially or totally fluorinated are usually chosen from processes chlorine-soda or fuel cells that consume hydrogen or methanol. Of such membranes are commercially available under such names as than NafionTM, FlemionTM, DowTM. Other similar membranes are proposed by Ballard Inc. in WO 97/25369, which discloses copolymers of tetrafluoroethylene and perfluorovinyl ethers or trifluorovinylstyrene. The monomers active at from which these copolymers are obtained carry chemical functions which are precursors of ionic groups of sulfonate or carboxylate type. Examples of these precursors are:

- -F2C = CF-0 CF2-IF-CF2-CF2-SO2F
X In F2C = CF-CF2 I F-O (CF2_ CO2CH3 X n or F2C = CF - {()} - THIRST
wherein -X is F, Cl or CF ,;

- n is 0 to 10 inclusive; and - p is 1 or 2;

Polyimide aromatic polymers or sulfonated polyether sulfones have also been considered, for example O S02X n or O

NONO
0 O S02X n Once obtained, the copolymer containing the aforementioned precursors is molded, for example in the form of sheets, then converted into ionic form by hydrolysis for give species of sulfonate or carboxylate type. The cation associated with anion

- 3 -sulfonate and carboxylate includes the proton, the cation of an alkali metal (Li, Ne, K); the cation of an alkaline earth metal (Mg2 +, Ca2 +, Bat +); the cation of a metal of transition (Zn2 +, Cul +); A13 +; Fei +; the cation of a rare earth (Sc3 +, Y3 +, Lai +); a organic cation of "onium" type, such as oxonium, ammonium, pyridinium, guanidinium, amidinium, sulfonium, phosphonium, these organic cations being optionally substituted by a or more organic radicals; an organometallic cation such as metallocenium arene-metallocenium, alkylsilyl, alkylgermanyl or alkyltin.

Such membranes, however, have several significant disadvantages.
A) Although the copolymers forming the membrane are insoluble in their form ionic, the membrane does not have good dimensional stability and swells way significant in water or polar solvents. These copolymers form micelles reversed only when heated at high temperature in a mixture specific water-alcohol, which, after evaporation, makes it possible to produce a film. However, this movie regenerated in solid form does not have good mechanical properties.

B) Tetrafluoroethylene (TFE) is a product whose handling is very risky because its polymerization is carried out under pressure and may cause controlled especially in the presence of oxygen. Because of the point difference boiling between the two monomers forming the copolymer and their polarity difference, it is difficult to obtain a statistical copolymer corresponding to the addition rate of each monomer.

C) The ionic groups in high concentration on the chain would have tendency to cause the solubilization of the copolymer. In order to prevent this phenomenon, concentration ionic groupings is kept at a low rate by adding a significant fraction

- 4 -molar monomers of TFE and / or increasing the length of the chains secondary (n> 1), with the result that the concentration of ion groups exchangeable is less than 1 milliequivalent per gram. As a result, the conductivity is relatively weak and very sensitive to the water content in the membrane, particularly when the latter is acidified for applications in a battery to combustible.

D) The penetration of methanol and oxygen through the membrane is high, since the perfluorocarbon portion of the polymer allows easy diffusion of cash molecules, which will chemically react with the opposite electrode and cause a loss Faradaic efficiency, mainly in fuel cells methanol.

Non-fluorinated systems such as sulfonated polyimides or polyethers sulphonated sulphones have the same disadvantages since it is necessary to compromise between the charge density, hence the conductivity, and the solubility or excessive swelling.
SUMMARY OF THE INVENTION

The present invention relates to a bifunctional monomer of formula General [T-SO2-Y-SOIT '] - M +
in which - T and T 'are identical or different and comprise an organic radical bringing to minus an active polymerization function such as unsaturation or cycle likely to open;

M + comprises an inorganic or organic cation;

- 5 -Y includes N or CQ wherein Q includes H, CN, F, SO 2 R 3, C, alkyl substituted or unsubstituted; Substituted or unsubstituted aryl; C, _20 alkylene substituted or not substituted, in which the substituent comprises one or more halogens, and in which the chain comprises one or more substituents F, SOIR, aza, oxa, thia or dioxathia; and R3 comprises F, C, substituted or unsubstituted alkyl; C, _20 aryl substituted or not substituted; Substituted or unsubstituted alkylene, in which the Substitute includes one or more halogens.

In a preferred embodiment, M + comprises the proton, the cation a metal such as an alkali metal, an alkaline earth metal, a rare earth or a metal of transition; an organometallic cation such as a metallocenium, an arena, metallocenium an alkylsilyl, an alkylgermanyl or an alkyltin; or an organic cation optionally substituted with one or more organic radicals. of the examples of Preferred organic cations include a group R "O + (onium), NR" +
(ammonium nium), R "C (NHR") 2+ (amidinium), C (NHR ") 3+ (guanidinium), CSR" N "(pyridinium), C3R "N2" (imidazolium), C2R "N3 + (triazolium), C3R" N2 + (imidazolinium), SR "
(sulf-onium), PR "'(phosphonium), IR" + (iodonium), (C6R ") 3C + (carbonium), in which R "
comprises:

proton, alkyl, alkenyl, oxaalkyl and oxaalkenyl radicals, azaalkyl, azaalkenyl, thiaalkyl, thiaalkenyl, dialkylazo, silalkyl optionally hydrolytically sand, silaalkenyl optionally hydrolysable, said radicals being to be linear, branched or cyclic and comprising from 1 to 18 carbon atoms;

WO 99/38842 _ 6 _ PCT / CA99 / 00083 aliphatic cyclic or heterocyclic radicals of 4 to 26 atoms carbon optionally comprising at least one side chain comprising one or many heteroatoms such as nitrogen, oxygen or sulfur;

aryls, arylalkyls, alkylaryls and alkenylaryls of 5 to 26 carbon atoms carbon optionally comprising one or more heteroatoms in the nucleus aromatic or in a substituent.

groups comprising a plurality of aromatic or heterocyclic rings, condensed or not, optionally containing one or more nitrogen atoms, oxygen, of sulfur or phosphorus;

and when an organic cation has at least two radicals R "different from H, these radicals may together form an aromatic ring or not, encompassing optionally the center carrying the cationic charge.

The invention further comprises an ion exchange and conductive polymer ion solid obtained from a monomer or a mixture of monomers bifunctional as defined previously. The monomer or monomer mixture may in outraged be copolymerized with at least one monofunctional monomer, preferably formula [T-SO3] -M + or [T-SO2-Y-SO, -W] -M + in which T, Y and M + are such than defined above, and W is a monovalent organic radical alkyl, alkenyl, aryl, arylalkyl, alkylaryl of 1 to 12 carbon atoms optionally carrying a or several substituents oxa, aza or thia.

The invention further relates to a process for preparing a polymer from monomers or monomer mixtures, in which the monomers or mixtures of monomers are polymerized in solution in a solvent, the formed polymer remaining homogeneously plasticized by the solvent. Monomers or mixtures of monomers are preferably polymerized as emulsions in solvents not miscible.

In the context of the process of the present invention, a radical initiator of polymerization can be added to the solution of the monomers. This initiator can be activated thermally or with actinic radiation. This initiator can also be a peroxide or an azo compound. Also, in the process of the present invention, an agent reinforcement can be added to the solution prior to polymerization and less a monomer monofunctional can be added.

The process of the present invention is particularly advantageous by report to methods of the prior art, since it makes it possible to obtain a polymer which remains plasticized homogeneously in the solvent. This phenomenon is rare and quite unexpected, and can be explained by the strong interactions between the charges and the solvent.

In addition, the invention further relates to an electrochemical cell comprising a membrane made with a polymer obtained from the process of this invention as solid electrolyte. Said cell may be one selected from a Fuel cell, a water electrolyser, a chlor-alkali battery, an electrochemical cell with recovery of salts or acid, or a battery producing ozone. Optionally, said cell electrochemical may comprise at least one electrode in contact with the said membrane.

Also, the invention relates to a polymer according to the present invention in a process chlorine-soda electrolysis, as a separator in a preparation electrochemical -7a-organic and inorganic compounds, as separator between an aqueous phase and an organic phase or as a catalyst for Diels-Alder additions, Friedel- reactions Craft, aldol condensation, cationic polymerization, esterifications and training acetals.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the use of perfluoro-di (vinyl ethers) wearing highly dissociated imide or sulphone functions, such as di (sulfonylmethane) or tri (sulfonylmethane), as a base for the production of exchange resin crosslinked ion obtained directly in a final form, for example a film or a fiber dig (here below commonly called "membrane"), and having a high density of ionic functions, resulting in increased conductivity. Polymerization can be driven in a concentrated solution of the monomer in salt form. Polymers obtained have the disadvantages of the perfluorinated ionomers of the prior art, since they have a good dimensional stability in the presence of solvents, including water and polar solvents, while maintaining excellent conductivity thanks to the high concentration of ionic groups. In addition, crosslinking forms an excellent barrier in front of the diffusion of molecular species, in particular oxygen or methanol, same as other organic fuels. The presence of TFE is not not necessary or can be minimized, thereby reducing the risks in the process of manufacturing. Polymers can be converted into extremely thin membranes thin, that is, with a thickness of about 50 m or less, while having a good mechanical strength, whereas conventional membranes of the same thickness have no mechanical strength. The process of the present invention thus represents a efficient use of monomers in terms of costs.

Electrochemical applications of membranes obtained from The crosslinked polymers of the present invention utilize electrodes and / or catalysts in intimate contact with the membrane serving as electrolyte.
During the use of these membranes, the electrode materials can be easily dropped on one or both sides of the membrane when it is made, and this possibly during the polymerization stage. Said materials Electrode can also be applied on an already formed membrane. This coating can be done by the application of a solution of at least one monomer according to this invention in a suitable solvent, followed by the polymerization, or by the application a solution or a suspension of a polymer possibly bearing functions Ionic. In all cases, the polymers present at the electrodes present advantageously the binder function of the active materials, conductors or catalysts.

In a preferred embodiment, the imide function, ie, when Y =
NOT, as well as polysulfonyl carbanions, and to a lesser extent anions perfluorosulfonate having a strong electronic affinity and being very dissociated, allow an increase in the catalytic activity of the cations, specific for several reactions.

_ 9 _ The polymers of the invention are therefore useful as a carrier for catalysts. Under form of a cross-linked material, the membrane or the material which composes it by example in the form of powder or granules, and containing the active cations in catalysis, are easily mechanically separated from the reaction medium once the reaction performed.

Examples of catalytic reactions include Diels-Alder, the Friedel-Craft reactions, aldol condensation, polymerizations cationic esterifications, formation of acetals etc.

Examples of preferred monomers include:

F2C = CF-CF2 iF-CF2-CF2 X In > F

X In CZ2 = CZ-;
CZ2 = CZ-E
denoted as:
CZ2 = CZ-E
O CZ2 = CZ-E
E-CZ = CZ2 wherein -X represents F, Cl, or CF3;

- n varies between 0 and 10 inclusively;
- E is absent, O, S, S02; and - Z is F or H.

The monomers of the invention can be obtained by different methods.
For example, the imide monomers are obtained as follows:

2 TSO2-L + [A2N] - Mi 2 LA + (TS02) 2N "M +
or TSO2-L + [T'AN] - M + LA + [(TSO2) N (SO2T ')] - M +

in which L is a leaving group, for example a halogen, a thiocyanate, or a an electrophilic group containing at least one heteroatom, such as N-imidazolyl, N-triazolyl, or R-S020- wherein R is C1-20 alkyl or C20 alkylene substituted or not substituted, wherein the substituent is one or more halogens; and in which the chain comprises one or more substituents selected from aza, oxa, thia, or dioxathia;
and A is the element or element moiety corresponding to the M + cation, and comprises hydrogen, a trialkylsilyl group, a trialkyltin group or tertioalkyl, wherein the alkyl group comprises from 1 to 6 carbon atoms.

In the same way, monomers composed of carbons, ie, when Y =
CQ, are obtained from similar reactions:

2 TSO, -L + [A2CQ] - M + = 2 LA + [(TSO2) 2CQ] - M +
in which L, T, Q, A and M are as defined above.

The tertioalkyl radical in the definition of A above is advantageous since it constitutes the precursor of an alkene eliminating from the middle reaction and a proton. For example, if it is a tertiobutyl, the following reaction is observed:

(CH3) 3C-Y => HY + (CH3) 2 = CH2 The trialkylsilyl group is advantageous when the leaving group L is fluorine, given the high enthalpy of formation of the Si-F bond.

When A is a proton or precursor of the proton, such as a radical tertiary alkyl, it is advantageous to carry out the reaction in the presence of a base cluttered, for example a tertiary base. Examples of such bases are the triethylamine the 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) or 1.8-diazabicyclo [5.4, O] undec-7-ene (DBU), guanidines such as tetramethylguanidine 1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido [1,2-a] pyrimidine (HPP).

In several cases, the potassium salt of the monomers of the invention are insoluble or very slightly soluble in water, and may be precipitated from more salts soluble, that is to say, the salts H +, Li 'or Na +, and subsequently purified by recrystallization.

The recrystallization can be carried out in water, alone or mixed with a solvent miscible, such as acetonitrile, dioxane, acetone or THF.

Alkylammonium salts, particularly tetraalkylammonium salts or imidazolium, are usually insoluble in water and can therefore be extracts to using various solvents, preferably halogenated, such as dichloromethane, the dichloroethane, trichloroethane, 1,1,1,2-tetrafluoroethane, etc.

It is understood that any function of the monomer that may interfere with the reaction leading to the formation of the bond S02-Y-SO2 is previously protected according to protection techniques well known to those skilled in the art. For example, the perfluorovinyl ether groups may be halogenated, in particular chlorinated or brominated to give a non-reactive perhaloether. Perfluorovinyl ether is optionally regenerated according to various methods well known to the person of career, for example, either by an electrochemical reaction or with a reduction like zinc powder, a zinc-copper bronze alloy, or the tetrakis (dimethylamino) ethylene.

The following bifunctional monomers illustrate preferred monomers of the invention.

M +
CF2 = CF -0 F2-F-CF2-CF2-SO2-N-SO2-CF2-CF2 I F-CF O-CF = CF2 X n X m M +
CF2 = CF-0 F2_ F-CF2-CF2-SO2 i-SO2-CF2-CF2 I F-CF O-CF = CF2 X n HX m M +
CF2 = CF-0 F2-F-CF2-CF2-SO2 i-SO2-CF2_CF2 I F-CF O-CF = CF2 X n SO2CF3 X m -FXF FF

M +
O F2-i F-CF2-CF2-SO2-N-S02-CF2 -CF2 - 1 FC FOF
X nx M
FXF FF
M +

X n QX m [CZ2 = CZS02-N-SO2CZ = CZ2] -M +
~~ M +
CF 2 = CF <)} - SO, - -SO2 - {()} - CF = CF2 M +
CF2 = CF - {()> _S02_E_s02 --- (() CF = CF2 j ~ M +
CF2 = CF-O- {()} -SO2-N-SO2 c -O-CF = CF2 CF2 = CF-O - ((- SO2-C-SO2 - ((} -O-CF = CF2 Q

in which M +, Z, Q, X and Y are as defined above, and n and m are identical or different and vary between 0 and 10 inclusive.

In practice, the ion exchange membranes are obtained by homo- or copolymerization of the bifunctional monomers of the present invention. For the copolymers, the comonomers are advantageously chosen from monofunctional monomers of general formula:

[T'-SO3] M +
or [T'-SO2-Y-SO2-W] -M +

-in which T ', Y, M + are as defined above, and W has the same definition Q.

Examples of preferred monofunctional monomers of the invention for copolymerization include:

CF2 = CF-O F2 IF OCF2-CF2-SO3 M +
X n M_ +
CF2 = CF-O F2_CF-OCF2-CF2-SO2-N-SO2-R ' X n M +
CF2 = CF-O F2-CF-O CF2-CF2-SO2-I-SO2-R ' XX
FxF

O F2 - i F-0 CF2-CF2-SO3M +
X in FxF

M +
CF2-CF-0 F2-CF2-SO2-N-SO2-R, X n pFxF
~ -I M +
F CF2-CF F2-CF2-SO2 SO2-R ' CF2 = CFSO3- M +

CF2 = CFSO3- M +
[CF2 = CFS 02-NS O2R '] -M +
CF2 = CF- {()} -SO3 M +

~ /
M_ +
CF2 = CF - (() y-SO2 N-SO2R
M_ +
CF2 = CF - (()} -SO2C-SO2R ' ~~ JI
CF2 = CF-O - (() --- SO2-M +
\ ~

M +
> ~ SO2-- -SO2R ' CF2 = CF-O - (M +
CF2 = CF-O- () r - SO2 - SO2R ' ~~ JQ
CF2 = CF-O F2-fF-O CF2- (CF2) - CO2 M + ' X ln FXF

FO CF2-CF-OF ~ (CF2) p-CO2-M
X n CF 2 = CF-_? _ coi m +
~ J
CF2 = CF-O- {(]} - CO2 M +

in which M, O, X and n are as defined above; R 'is a organic radical monovalent comprising from 1 to 12 carbon atoms, preferably perfluorinated, optionally having one or more substituents oxa, aza, thia or dioxathia; and p is 1 or 2.

Advantageously, the polymerization and copolymerization reactions are make in a solvent of the monomers. These are generally soluble in the most conventional polar solvents, ie, water, lower aliphatic alcohols, acetone, methyl ethyl ketone, cyclic ketones, ethyl and propyl carbonates, y-butyrolactone, glymes, alkylpyralidones, tetraalkylamines, dichloromethane, N-alkylimidazole, fluoroalkanes, fluorinated hydrocarbons and mixtures thereof. In addition, the choice of M allows to optimize the solubility of the monomers, thanks to the cation-solvent interactions. It is heard only after the polymerization has been completed, the exchanges of M take place according to techniques Conventional used in the field of ion exchange resins. of the additives organic or inorganic solids, in the form of powder or fiber, may to be added to the manufacturing step to improve the mechanical properties of the polymers, act like pig formation agent, or as a catalyst support (eg, platinum filed on carbon particles).

The following examples are provided to illustrate embodiments of the invention and should in no way be interpreted as by limiting the scope.

Examples Example 1 Under a nitrogen atmosphere, 25 g of p-iodobenzene sulphonyl chloride are treated with 1.44 g of lithium nitride in 125 ml of anhydrous DMF. After 24 hours of reaction with constant mechanical stirring, the reaction mixture is filtered and the solvent is evaporated under reduced pressure at 80 ° C. The solid residue containing the sodium salt lithium of 4-iodophenylsulfonimide is dissolved in 100 ml of water, filtered and acidified by acid sulfuric acid until a pH of 1 is reached. 4-Iodophenylsulfonimide is extracted by four aliquots of 100 ml of ether, the organic phases are subsequently combined and the ether is evaporated. 4-iodophenylsulfonimide is purified by crystallization in water and zinc salt is prepared by action of zinc carbonate in quantity stoichiometric. The salt is dried under vacuum at 80 ° C.

The organozinc CF 2 = CFZnBr is prepared under argon in DMF according to procedure published in J. Organic Chemistry, 53, 2714, (1988) from CF2 = CFBr (10 g) in a thermostated reactor. 18 g of the zinc salt as prepared previously in the DMF are added to the organometallic solution mixed with 160 mg of benzylideneacetone palladium (0) and 190 mg of triphenylphosphine acting as co-catalyst, keeping the temperature below 65 C. The reaction is continued for 4 hours at this temperature and the solvent is evaporated under pressure reduced to C. The solid residue is taken up in water, filtered and treated with 10 g of carbonate of potassium in 100 ml of water. The white suspension containing the carbonate of zinc is evaporated under reduced pressure at 60 C. The potassium salt is extracted by mixed acetonitrile-dimethoxyethane (50:50 v / v), and the solvent is evaporated. Salt from potassium:

CF2 \ K + 0 CF -NI O

is purified by recrystallization from water and converted into lithium salt by double exchange with lithium tetrafluoroborate in acetonitrile in which KBF4 is insoluble.

Example 2 A solution of 1 g of the lithium salt of Example 1, 10 g of 4-lithium trifluorovinylbenzene sulfonate, 250 mg of Irgacure 651 in 35 ml a mixture of propylene carbonate and diglyme (bis [methoxyethylether]) (50:50 v / v) are spread using a template in the form of 180 micron film thick on a polypropylene support. Under argon sweep, the solution submitted to influence UV produced by a Hanovia type lamp having its maximum emission at 254 nanometers so that the illumination corresponds to 80 mWcm 2.
solution then polymerizes in the form of an elastic gel. The polymerization is continued for 5 minutes then the film is peeled off its support and washed with water then with acid nitrate 2M at 60 C to remove organic solvents and residues from polymerization. The conductivity of the membrane measured between 60 and 100%
humidity is greater than 102 Scm- '. The dimensions of the membrane are stable in a great relative humidity range because of the high concentration of nodes of crosslinking.

Example 3 * rB

-30 g of 4-iodobenzenesulfonyl chloride, 15 g of trifluoromethane-sulfonamide and 23 g of 1,4-diazabicyclo [2,2,2] octane are dissolved in 200 ml of anhydrous acetonitrile and kept under magnetic stirring for 48 hours.
hours at 25 C.
The suspension is filtered and the acetonitrile is evaporated. The solid residue is taken over by the minimum of water to which 100 ml of saturated KCl solution is added. The precipitated salt of potassium is filtered off and purified by recrystallization from the boiling water.
In a manner similar to that of Example 2, the para-iodine is replaced by CF 2 CF group by coupling of the organozinc CF 2 = CFZnBr in the presence of catalyst based on palladium. Potassium salt CF2 \ 0 K + - 0 He He O

is purified by recrystallization from water and converted into lithium salt.
A solution of 8.8 g of this salt and 1 g of the monomer of Example 1 in the form of lithium salt are dissolved in 40 ml of y-butyrolactone, spread as a film of 150 microns thickness on a polypropylene support and polymerized under the conditions of Example 2. The film is peeled off its support and washed with water and with acid nitric 2M to 60 C so as to eliminate the y-butyrolactone and carry out the exchange Li '=>>
H +. On the one similar way, the mixture of salts in identical proportions in the y-butyrolactone suspension in decane are polymerized with tridecylmethyl persulfate ammonium acting as surfactant and generator of free radicals at 60 C.
A latex particle size close to 20 gm is thus obtained, separated by filtration and treated as before to perform the exchange Li '= H +.

-Example 4 50 g of perfluorovinyloxy-ethanesulfonyl fluoride CFZ CFOCF2CF2SO2F
in 300 ml carbon tetrachloride are treated with an excess of chlorine in one quartz container under UV illumination. The adduct on the double bond CF 2 (Cl) CF (Cl) OCF 2 CF 2 SO 2 F is purified by distillation. In a container thick-walled high-density polyethylene (Nalgene) are added 35 g of CF 2 (Cl) CF (Cl) OCF 2 CF 2 SO 2 F as previously prepared, 125 ml of anhydrous THF
and 1.74 g of lithium nitride and 36 zirconia milling rolls (@ 1 cm3).
After 24 hours of stirring in a roller mill, 10 g of zinc-zinc alloy copper (10%
Cu) are added and stirring is continued for 24 hours additional. The final product is filtered and the solvent is evaporated under reduced pressure at 40.degree.
C. The residue is taken up with a 10% solution of potassium chloride in water. The precipitate is washed, filtered and recrystallized from a water-ethanol mixture (50:50 v / v). Salt from lithium Li [(CF 2 CFOCF 2 CF 2 SO 2) 2 N] is obtained by LiBF 4 exchange in the triglyme.
The perfluorovinyloxy-ethylsulfonate of CF2 = CFOCF2CF2SO3Li lithium is prepared by a similar procedure from perfluorovinyloxy fluoride ethanesulfonyl by treatment with lithium trimethylsilanoate in the triglyme and filtered.

Example 5 A perfluorinated crosslinked membrane is prepared in homogeneous phase by copolymerization of 4 g of lithium salt Li [(CF2 = CFOCF2CF, SO2) 2N] from example 4, -with 24 g of lithium perfluorovinyloxy ethanesulphonate in 60 ml of triglyme. 1.5 g fumed silica nanoparticles (average size 70 A) are added and scattered under mechanical stirring in a ball mill. The radical initiator is the peroxide of trichloroacetyl in a proportion of 1 mol% relative to the monomers. The solution is spread on a polypropylene support so as to form a film of 100 microns thick. The polymerization / crosslinking step is obtained by heating at 80 C under deoxygenated nitrogen atmosphere. The film obtained is taken off its support and washed in water and 2M nitric acid at 60 ° C to remove organic solvents and residues as well as to carry out the replacement of the Li 'cations with H +.
The The conductivity of the membrane at 95% humidity is about 10 'Scm'. The permeation methanol is an order of magnitude smaller than a membrane from Nafion 117 of similar thickness.

Example 6 17.5 g of perfluorovinyloxy ethanesulfonyl fluoride CF2 (C1) CF (C1) OCF2CF2SO2F treated with chlorine under UV radiation are paid in a container of Nalgene and are added 100 ml of anhydrous THF and 1.2 g of carbide of C3A14 aluminum and 36 zirconia grinding cylinders (approx.
cm3). After 48 hours of stirring in a roller mill are added 10 g of powder zinc and stirring is continued for another 48 hours. The final product is filtered and the The solvent is evaporated under reduced pressure at 40 ° C. The residue is taken up by a solution to 10% potassium chloride in the water. The precipitate is washed, filtered and recrystallized in a water-ethanol mixture (50:50 v / v). By exchange with LiBF4 the salt of Li lithium [(CF, = CFOCF, CF, SO,), CH] is obtained. This difunctional monomer can himself * rB

polymerize in a manner similar to that of Example 4, and is advantageously used when strongly acidic but little hygroscopic functions are preferred.

Example 7 Perfluoro (4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride (Synquest Research Chemicals FI, USA) is treated with lithium nitride in conditions of Example 4 after protection of the double bond by bromine. Salt from lithium Li [(CF2 = CFOCF, CF (CF3) OCF2CF2SO2) 2N] is obtained after reduction with zinc and purification at the stage of the potassium salt obtained as intermediate. The perfluoro (4-lithium methyl-3,6-dioxaoct-7-ene) sulfonate is obtained in a manner similar by reaction of lithium silanoate with sulfonyl fluoride in the dibutyldiglyme ([C4H9OC2H4] 2O). A crosslinked membrane is obtained by polymerization of a mixed 3 g of the divinyl monomer and 18 g of the monovinyl perfluorosulphonate, 800 mg of fumed silica (7 nm) in 50 ml of dibutyldiglyme. The solution is spread form of film and the polymerization is carried out using the photoinitiator Irgacure 651. Under argon sweep, the solution subjected to UV radiation under the conditions of Example 2. The membrane is washed with ethanol and then with water and the ions lithium are exchanged with 5M HCl in water.

Example 8 Perfluoro (4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride of Example 7 is treated with aluminum carbide under the conditions of Example 6.
After treatment by the potassium carbonate and removal of the formed aluminum hydroxide, the salt of Lithium Li [(CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF, SO 2) 2 CH] is obtained after purification of salt -of potassium and exchange in the presence of LiBF4 in THF. Results similar are obtained by using instead of aluminum carbide Nysted's reagent (Zn3Br2 (CH2) 2, THF). Like its nitrogen analogue, this monomer is likely to homopolymerize or to copolymerize with tetrafluoroethylene or monofunctional monomers Ionic. A copolymer crosslinked with perfluoro (4-methyl-3,6-dioxaoct-7-ene) lithium sulfonate (10: 90 molar) is obtained in a manner similar to that of Example 7.

Example 9 To 3.73 g of trifluoromethylmethylsulfone CF3SO2CH3 in 50 ml of TI-IF are added at 0 ° C. 600 mg of sodium hydride and then 3.15 ml of chlorotrimethylsilane. After precipitation of the sodium chloride formed, the supernatant liquid is filtered and are added ml of a 2.5 M solution of butyllithium in hexane. The addition product of chlorine on the CF2 (Cl) CF (Cl) double vinyl bond OCF2CF2SO2F is prepared as for Example 4 In a high density polyethylene container with walls thick (Nalgene) are added the dilithiated derivative of the sulfone in THF as prepared, 6.7 ml of tetramethylethylenediamine (TMDA) and 17.5 g of CF2 (Cl) CF (C1) OCF2CF2SO2F
obtained by the addition of chlorine to the double bond of perfluorovinyloxy-ethanesulfonyl in a manner similar to that of Example 4. 36 grinding cylinders in zirconia (About 1 cm ') are included to promote the solid-heterogeneous reaction.
liquid. After 24 hours of stirring in a roller mill, 5 g of zinc-zinc alloy copper (10%
Cu) are added and stirring is continued for 24 hours additional. The final product is filtered and the solvent is evaporated under reduced pressure at 40.degree.
C. The residue is taken up with a 10% solution of potassium chloride in water. The precipitate is washed, filtered and recrystallized from a water-ethanol mixture (50:50 v / v). Salt from Li [(CF2CFOCF2CF2SO2) 2CSO2CF3 lithium is obtained by LiBF4 exchange in the triglyme. Monofunctional monomers bis (trifluomethanesulfonyl) (tri fluoperfluorovinyloxy-ethylsulfonyl) lithium methylide Li [CF2 CFOCF2CF2SO2C (SO2CF3) 2 and trifluomethanesulfonyl-(trifluoperfluorovinyloxy-Lithium ethylsulfonylimide Li [CF2 = CFOCF2CF2SO2N (SO2CF3) can be got in a similar manner by the action of CF 2 (Cl) CF (Cl) OCF, CF 2 SO 2 F prepared at example 4 on dilithiated derivatives of Li2C (SO2CF3) 2 disulfone and sulfonamide Li2NSO2CF3 respectively.

Example 10 From perfluoro (4-methyl-3,6-dioxaoct-7-ene) sulfonyl fluoride Example 8 are obtained by reacting the reagents of Example 9:

Li [(CFOC CFOCF 2 CF (CF 3) OCF 2 CF 2 SO 2) 2CSO 2 CF 3] difunctional;

Li [CF2 = CFOCF2CF (CF3) OCF2CF2SO2C (SO2CF3) 2] monofunctional;
Li [CF2 = CFOCF2CF (CF3) OCF2CF2SO2N (CSO2CF3)] monofunctional.

These monomers make it possible to prepare crosslinked copolymers incorporating minus the difunctional monomer and one of the monofunctional monomers selected from those of the Examples 7, 9 or 10 having in common perfluorovinyl ether functions of reactivity identical.

Example 11 The salt of Example 7 Li [(CF 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 SO 2) 2 N] is treated with chloride 1-methyl-3-ethyl-imidazolium dissolved in water. A viscous liquid is decanted and is extracted with dichloromethane to give [(CF2 = CFOCF2CF (CF3) OCF2CF2SO2) 2N] "
~ N \

According to the same method, the monofunctional sulfonate:

1 1 CF2 = CFOCF2CF (CF3) OCF2CF2SO3 is prepared by exchange in water, as well as the radical initiator salt azobis (2-imidazolidium-2-methyl-propane):

2 CF2 = CFOCF2CF (CF3) OCF2CF2SO3 HH
C + NN C

HH

The salts are mixed in molar ratios 8: 91: 1 monomer bifunctional monofunctional monomer: radical initiator. The viscous mixture is spread on a polypropylene sheet maintained at 40 C so as to form a layer of 35 m thick and the whole is brought to 80 C for 2 hours under scanning nitrogen. The obtained membrane is peeled off its support and the polymerization is completed by two hours of treatment at 100 C. The imidazolium ions are exchanged by the ions sodium by treatment with 1 M sodium hydroxide solution in refluxing ethanol during 4 hours, causing degradation of the organic cation. The sodium ions are at their turn exchanged by protons by immersion in a Soxhlet extractor by solution aqueous hydrochloric acid to the azeotropic composition (20.3% by weight).
The same difunctional monomer is copolymerized with the monofunctional monomer of Example 10, Li [CF2 = CFOCF2CF (CF3) OCF2CF2SO2N (CSO2CF3)] and the initiator radical previously used. The copolymerization is carried out in inverse emulsion in the decalin with strong mechanical stirring, the ratios of the components assets being now 25: 74: 1. The system is purged with argon and after two hours at 90 C, the polymer beads are separated by filtration, washed and exchanged as previously.
Example 12 17.5 g of commercial 4-hydroxybenzene sulfonic acid are treated with 4 ml 4M soda in water. The salt is dried on a rotary evaporator and then Azeotropic dehydration. 19.5 g of the salt obtained Na2 (O (DSO3) (0 = para -C6H4-) are suspended in 100 ml of DMF with 10.75 ml of 1,2-dibromo tetrafluoroethane and the mixture is heated to 80 ° C. in a Parr reactor purged with nitrogen at previous under argon and the reaction is continued for 4 hours. Salt Na (BrCF2CF20'DSO3) is filtered off and the sulfonyl chloride is prepared by the action of chloride of thionyl in acetonitrile catalyzed by DMF. The imide Na (BrCF2CF20'DSO2) N is prepared at 0 ° C. by addition of sodium hydroxide to a suspension of the acid chloride in one aqueous solution of ammonium chloride according to the equation 2 BrCF2CF20'DSO2C1 + NH4Cl + 4 NaOH = 3 NaCl + 2H2O + Na (BrCF2CF2O'DSO2) 2N
In a thick-walled high-density polyethylene container (Nalgene) 14 g (709.15023) of Na-imide (BrCF2CF20'DSO2) 2N are added, such that prepare -previously, 100 ml of anhydrous DMF and 4 g of zinc alloy powder and 25 cylinders of grinding zirconia (about 1 cm3). After 24 hours of agitation in a grinder rollers, the solvent is evaporated under reduced pressure at 80 C. The residue is taken over by saturated solution of potassium chloride in the water and the precipitate of K (CF2CF2O (tSO2) 2N is purified by crystallization in water This salt can be polymerize by radical or thermal initiation or be included in a copolymer with the monomer Na (CF2CF2O (DSO3) obtained by zinc reduction of Na (BrCF2CF2O (DSO3).
Example 13 An experimental fuel cell is made from a membrane prepared in Example 3. A nanometric dispersion of platinum on a support of carbon (Degussa, Germany) is applied on both sides of the membrane by a technical screen printing from a dispersion of platinum carbon in a solution colloidal (5% w / w) Nafion 117 in a mixture of light alcohols (Aldrich). The system is treated at 130 C by applying a pressure of 20 Kgcm 2 to ensure the cohesion Nafion particles. A collector of carbon paper (fiber felt from carbon non-woven material) is interposed between the electrodes and the current collectors in steel grooved stainless to ensure the distribution of gases. The experimental pile is tested with a supply of hydrogen saturated with water vapor at 80 C and oxygen both gas being at ordinary pressure. The open circuit voltage is 1.2 V and the curve measured voltage current on this mount indicates 1 Acm'2 are obtained at the voltage of 0.65 V.

Example 14 WO 99/38842 - 28 _ PCT / CA99 / 00083 An experimental fuel cell is made from a membrane prepared in Example 5. The platinum carbon electrode is applied from and other of the screen-printed membrane of a suspension (30% by weight) of this material in solution in the diglyme comprising A) 15% by weight of the monomer of Example 4 Li [(CF 2 CFOCF 2 CF 2 SO 2) 2 N]; B) 15% of the monofunctional monomer of Example 10 Li [CF2 = CFOCF2CF (CF3) OCF2CF2SO2N (CSO2CF3)]; and C) 1% by weight of the initiator of example 11.

The polymerization of the monomer of the electrode is obtained by heating under nitrogen atmosphere at 90 C for two hours. The electrode assembly /
membrane is rinsed abundantly in a 2M aqueous hydrochloric acid solution for remove organic solvents, unreacted monomer and oligomers, so that to ensure the exchange of ions Li 'of the polymer of the electrode by protons.
The battery experimental fuel using this assembly has a circuit voltage open of 1.2 V and the voltage current curve measured on this circuit shows 1 Acm 2 are obtained at the voltage of 0.72 V. The replacement of the platinum of the negative electrode by a alloy platinum-ruthenium 50:50 allows the use as methanol fuel with a current density of 150 mAcm 2 at a voltage of 0.6 V to 100 C.
permeation of methanol under these conditions is less than 5 gmoles.cm 2s'.

Example 15 The electrode / electrolyte assembly of an experimental fuel cell is made in a single step by coextrusion of the corresponding three layers form monomers undergoing co-polymerization / crosslinking. The central part is a dispersion of silica nanoparticles (1.5 g) in a solution of Li [(CFOC CFOCF 2 CF 2 SO 2) 2N] (4 g), Li [(CF 2 = CFOCF 2 CF 2 SO 3) (24 g) in 40 ml of triglyme and 1 g of the radical initiator of Example 11. The electrodes are formed a platinum carbon dispersion (10 g), of granular calcium carbonate micron (10 g), of Li [(CF 2 CFOCF 2 CF 2 SO 2) 2 N], (2 g), Li [(CF 2 CFOCF 2 CF 2 SO 3) (12 g) in 40 ml of triglyme and 0.8 g of the initiator radical of example 11. The extrusion thicknesses are adjusted to 60 m for the electrolyte and 30 gm for each of the electrodes. The polymerization is immediately carried out after extrusion by heating at 80 ° C. for 4 hours under nitrogen. The assembly is treated in a Soxhlet apparatus with hydrochloric acid in the composition azeotropic to exchange the metal ions. The dissolution of calcium carbonate creates a porosity favorable to gaseous exchange of the electrodes. The assembly extruded as well may be cut to size to form from stack to modular fuels by addition of current collectors and feeders gas.

Example 16 Electrolysis of sodium chloride is carried out in a two-cell compartments separated by a membrane as prepared in Example 7, the anode being of the DSA type (Dimensionally Stable Electrode) and made of titanium covered with a ruthenium oxide RuO2 layer in contact with the membrane, the cathode being in nickel. The ohmic drop for 2 Acm 2 is 0.4V and the permeation of OH-at through the membrane is less than 9 gmoles.cm "2s'.

Example 17 The membrane of Example 4 is used for the preparation of ozone by electrolysis of water on an anode of lead dioxide, the cathode is a grid of platinum, the two electrodes being pressed onto the membrane whose side cathodic is immersed in water. Faradic efficiency in ozone and 24% under 5V.

Example 18 The porous ion exchange resins prepared in Examples 3 and 11 are used as catalysts for chemical reactions. Protonic form active after vacuum dehydration, the resin catalyzes the reactions of Friedel and Craft, the esterifications, acetalisations etc. Has an equimolecular mixture anisole and of acetic anhydride are added 3% by weight of the resin of Example 3 under form acid. The formation reaction of 4-methoxyacetophenone is complete in 45 minutes at ordinary temperature.

Proton exchange for transition ions and earth metals rare, in particular La + 3 and Y + 'gives a catalyst for Friedel reactions and Craft and cross-aldolization. To an equimolecular mixture of cyclopentadiene and vinyl methyl ketone (10 mmol in 30 cc of dichloromethane are added 5% by weight of the resin of Example 11 in Y3 + form and dried under vacuum at 60 C. The reaction of training of Diels-Alder condensation compound is complete at 25 C in 30 minutes, the report endo / exo being close to 90:10.

In both cases, the catalyst is removed by simple filtration and reusable.

Although the present invention has been described using implementations specific, it is understood that several variations and modifications may add to implemented, and the present application is intended to cover such changes, uses or adaptations of the present invention according to, in general, the principles of invention and including any variation of the present description which will become known or Convention in the field of activity in which this invention, and which can be applied to the essential elements mentioned above, in agreement with the scope of the following claims.

Claims (34)

1. Bifunctional monomer of general formula [T-SO2-Y-SO2T '] - M +
in which - T and T 'are identical or different and include CZ2 = CZ-;

wherein :
X comprises a halogen or CF3;
- n varies between 0 and 10 inclusively;
- E is absent, O, S, or SO2; and - Z is F or H

M + comprises a proton, a metal cation, an organometallic cation or a cation organic;

Y comprises N or CQ wherein Q comprises H, CN, F, SO2 R3, C1-20 alkyl substituted or unsubstituted; Substituted or unsubstituted C1-20 aryl; C1-20 alkylene substituted or not substituted, in which the substituent comprises one or more halogens, and in which the chain comprises one or more substituents F, SO2R3, aza, oxa, thia or dioxathia; and - R3 comprises F, C1-20 alkyl substituted or unsubstituted; C1-20 aryl substituted or not substituted; C1-20 substituted or unsubstituted alkylene, in which the substituent includes a or more halogens. The monomer of claim 1 wherein the metal cation comprises a metal alkali, an alkaline earth metal, a rare earth or a transition metal;
the cation organometallic composition comprises a metallocenium, an arene-metallocenium, a alkylsilyl, a alkylgermanyl or an alkyltin; and the organic cation comprises a group R "O +
(onium), NR "+ (ammonium), R" C (NHR ") 2+ (amidinium), C (NHR") 3+ (guanidinium), C5R "N + (pyridinium), C3R" N2 + (imidazolium), C2R "N3 + (triazolium), C3R" N2 +
(imidazolinium), SR "+ (sulfonium), PR" + (phosphonium), IR "+ (iodonium), (C6R ") 3C +
(carbonium), wherein R "comprises:

the proton, the alkyl, alkenyl, oxaalkyl and oxaalkenyl radicals, azaalkyl, azaalkenyl, thiaalkyl, thiaalkenyl, dialkylazo, silalkyl optionally hydrolysable, silaalkenyls optionally hydrolyzable, said radicals can be linear, branched or cyclic and comprising from 1 to 18 carbon atoms;

aliphatic cyclic or heterocyclic radicals of 4 to 26 atoms carbon optionally comprising at least one side chain comprising one or many heteroatoms;

aryls, arylalkyls, alkylaryls and alkenylaryls of 5 to 26 carbon atoms including carbon optionally one or more heteroatoms in the aromatic ring or in a substituent;

groups comprising a plurality of aromatic or heterocyclic rings, condensed or not, optionally containing one or more nitrogen, oxygen, sulfur atoms or phosphorus;

and when an organic cation has at least two radicals R "different from H, these radicals may together form an aromatic ring or not, encompassing optionally the center carrying the cationic charge. 3. The monomer according to claim 2 wherein said heteroatom is of nitrogen, oxygen or sulfur. The monomer of claim 1 wherein the monomer comprises:
as well as their mixtures. 5. Ion exchange polymer obtained from a monomer or a mixture of monomers according to claim 1. The polymer of claim 5 wherein the bifunctional monomer is copolymerized with at least one monofunctional monomer. The polymer of claim 6 wherein the monofunctional monomer is of formula [T-SO3] -M + or [T-SO2-Y-SO2-W] -M + in which T, Y and M + are such that defined in claim 1 and W is a monovalent organic radical alkyl, alkenyl, aryl, arylalkyl, alkylaryl of 1 to 12 carbon atoms optionally carrying a or many oxa, aza or thia substituents. The polymer of claim 6 wherein at least one monomer monofunctional is of formula:

and mixtures thereof, and wherein p = 1 or 2; M and Y are as defined in claim 1 and n is as defined in claim 4, X comprises a halogen or CF3 and R 'comprises a monovalent organic radical comprising from 1 to 12 carbon atoms, optionally partially or totally fluorinated, and optionally substituted with one or several oxa, aza, thia, or dioathia. 9. Process for preparing a polymer from monomers or mixtures of monomers according to claim 1, wherein the monomers or mixtures of monomers are polymerized in solution in a solvent, the polymer formed remaining laminated one way homogeneous by the solvent. The process according to claim 9 wherein the monomers or mixtures of monomers are polymerized as an emulsion in an immiscible solvent. The method of claim 9 wherein the solvent comprises water, a alcohol lower aliphatic, acetone, methyl ethyl ketone, cyclic ketones, the carbonates ethyl and propyl, γ-butyrolactone, glymes, N-alkylpyrrolidones, tetraalkylsulfamides, dichloromethane, N-alkylimidazole, fluorinated hydrocarbons, or their mixtures. The method of claim 9 wherein a radical initiator of polymerization is added to the monomer solution. The method of claim 12 wherein the initiator is enabled.
thermally or using actinic radiation. The process of claim 13 wherein the initiator is a peroxide or one azo compound. The method of claim 9 wherein a reinforcing agent is added to the solution before polymerization. The process of claim 9 wherein at least one monomer monofunctional is added. 17. The method of claim 16 wherein the monomer is of formula [T-SO3] M + or [T-SO2-Y-SO2-W] M + in which T, Y and M + are as defined and W is a monovalent organic radical alkyl, alkenyl, aryl, arylalkyl, alkylaryl from 1 to 12 carbon atoms optionally carrying one or more oxa substituents, aza or thia. 18. Solid ion conductor obtained from a monomer or a mixture of monomers according to claim 1. The ion solid conductor of claim 18 wherein the monomer bifunctional is copolymerized with at least one monofunctional monomer. The ion solid conductor of claim 19 wherein the monomer monofunctional is of formula [T-SO3] -M + or [T-SO2-Y-SO2-W] -M + in which T, Y and M + are as defined in claim 1 and W is an organic radical monovalent alkyl, alkenyl, aryl, arylalkyl, alkylaryl of 1 to 12 carbon atoms bearing optionally a or more substituents oxa, aza or thia. The solid ion conductor of claim 19 wherein at least one monofunctional monomer is of formula:

CF2 CF-SO3-M +; or CF2 = CF-O-CF2CF2SO, -M +;
CF2 CF-O-CF (CF3) CF2O-CF2CF2SO3-M ';

and mixtures thereof, and wherein p = 1 or 2; M and n are as defined in claim 1, X comprises a halogen or CF 3 and R 'comprises an organic radical monovalent comprising from 1 to 12 carbon atoms, optionally partially fluorinated or in full, and optionally substituted with one or more oxa, aza, thia, or dioathia. 22. Process for preparing a solid ion conductor from monomers or monomer mixtures according to claim 1, wherein the monomers or mixtures of monomers are polymerized in solution in a solvent, the polymer formed remaining plasticized homogeneously by the solvent. 23. The method of claim 22 wherein the monomers or mixtures of monomers are polymerized as an emulsion in an immiscible solvent. 24. The method of claim 22 wherein the solvent comprises water, an alcohol lower aliphatic, acetone, methyl ethyl ketone, cyclic ketones, the carbonates ethyl and propyl, γ-butyrolactone, glymes, N-alkylpyrrolidones, tetraalkylsulfamides, dichloromethane, N-alkylimidazole, fluorinated hydrocarbons, or their mixtures. 25. The method of claim 22 wherein a radical initiator of polymerization is added to the monomer solution. The method of claim 25 wherein the initiator is enabled thermally or using actinic radiation. 27. The method of claim 26 wherein the initiator is a peroxide or one azo compound. 28. The method of claim 22 wherein a reinforcing agent is added to the solution before polymerization. 29. The method of claim 22 wherein at least one monomer monofunctional is added. 30. The method of claim 29 wherein the monomer is of formula [T-SO 3] M +
or [T-SO2-Y-SO2-W] M + in which T, Y and M + are as defined and W is a radical organic monovalent alkyl, alkenyl, aryl, arylalkyl, alkylaryl of 1 to 12 atoms of carbon optionally bearing one or more substituents oxa, aza or thia. 31. Electrochemical cell comprising a membrane made of a polymer obtained from the process according to any one of claims 9 to 17, as solid electrolyte. 32. The cell of claim 31 which is a fuel cell, a water chlorinator, a chlor-alkali battery, an electrochemical cell with salt recovery or acid, or a battery producing ozone. The cell of claim 31 wherein at least one electrode is in touch with the membrane. 34. Use of a polymer according to claim 5 in a process electrolysis chlorine-soda, as a separator in an electrochemical preparation of compounds organic and inorganic, as a separator between an aqueous phase and a phase organic, or as a catalyst for Diels-Alder additions, reactions Friedel-Craft, aldol condensation, cationic polymerization, esterifications, and Training acetals.