Cross-linkable bi-sulphonyl derivatives and their uses for preparing ion-exchanging membranes

Abstract

The present invention is concerned with novel ion-exchange membranes, their method of preparation and their uses. The membranes are made of a polymer obtained from a monomer or a mixture of bifunctional monomers of general formula [T-SO 2 —Y—SO 2 T 1 ] − M + . The polymers are useful in an alkali-chloride electrolysis process, as a separator in an electrochemical preparation of inorganic and organic compounds, as a separator between an aqueous and an organic phase, or as a catalyst for Diels-Alder additions, Friedel-Craft reactions, aldol condensations, cationic polymerizations, esterifications, and acetal formations.

1 . A bifunctional monomer of general formula:  
         [T-SO 2 —Y—SO 2 T′] − M +   
       wherein 
 T and T′ are the same or different and comprise an organic radical bearing at least one polymerization active function such as an insaturationor a cycle susceptible of opening;  
 M + comprises an inorganic or organic cation;  
 Y comprises N or CQ wherein Q comprises H, CN, F, SO 2 R 3 , C 1-20  alkyl substituted or unsubstituted; C 1-20  aryl substituted or unsubstituted; C 1-20  alkylene substituted or unsubstituted, wherein the substituent comprises one or more halogens, and wherein the chain comprises one or more substituents F, SO 2 R, aza, oxa, thia or dioxathia; and  
 R 3  comprises F, C 1-20  alkyl substituted or unsubstituted; C 1-20  aryl substituted or unsubstituted; C 1-20  alkylene substituted or unsubstituted, wherein the substituent comprises one or more halogens.  
 
     
     
         2 . Monomer according to  claim 1 , wherein M + comprises the proton, a metallic cation, an organometallic cation or an organic cation optionally substituted with one or more organic radicals.  
     
     
         3 . Monomer according to  claim 2 , wherein the metal comprises an alkaline, an alkaline-earth metal, a rare earth or a transition metal; the organometallic cation comprises a metallocenium, an arene-metallocenium, an alkylsilyl, an 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), C 5 R″N +  (pyridinium), C 3 R″N 2   +  (imidazolium), C 3 R″N 2   +  (triazolium), C 3 R″N 2   +  (imidazolinium), SR″ +  (sulfonium), PR′ +  (phosphonium), IR′ +  (iodonium), (C 6 R″) 3 C +  (carbonium), wherein R″ comprises: 
 a proton, an alkyl, an alkenyl, an oxaalkyl, an oxalkenyl, an azaalkyl, an azaalkenyl, a thiaalkyl, a thiaalkenyl, a dialkylozo, a silaalkyl, optionally hydrolysable, a silaalkenyl optionally hydrolysable, leach of these being straight, branched or cyclic and comprising from 1 to 18 carbon atoms;    aliphatic heterocyclic or cyclic radicals comprising from 4 to 26 carbon atoms comprising optionally at least one lateral chain comprising one or more heteroatoms such as nitrogen, oxygen or sulfurs;    an aryl arylalkyl, alkylaryl or alkenylaryl of from 5 to 26 carbon atoms optionally comprising one or more heteroatoms in the aromatic nucleus or in a substituent;    groups comprising several heterocyclic or aromatic nuclei, condensed or not, optionally containing one or more nitrogen, oxygen, sulfur or phosphorus;    and when an organic cation comprises at least two radicals R″ different from H, these radicals can form together a cycle aromatic or not, optionally containing the center bearing the cationic charge.    
     
     
         4 . Monomer according to  claim 1 , wherein T and T′ are the same or different and comprise:  
       
         
           
           
               
               
           
         
       
       wherein: 
 X is a halogen or CF 3 ;  
 n varies between 0 and 10 inclusively;  
 E is absent, O, S, SO 2 ; and  
 Z is F or H.  
 
     
     
         5 . Monomer according to  claim 1 , wherein the monomer comprises:  
       
         
           
           
               
               
           
         
       
       and mixtures thereof.  
     
     
         6 . An ion exchange and solid ion conductor polymer obtained from a monomer or a mixture of monomers according to  claim 1 .  
     
     
         7 . A polymer according to  claim 6 , wherein the bifunctional monomer is copolymerized with at least one monofunctional monomer.  
     
     
         8 . A polymer according to  claim 7 , wherein the monofunctional monomer is of formula [T-SO 3 ] − M +  or [T-SO 2 —Y—SO 2 —W] − M +  wherein T, Y, M +  are as defined above, and W is a monovalent organic radical alkyl, alkenyl, aryl, arylalkyl, alkylaryl of 1 to 12 carbon atoms optionally bearing one or more substituents oxa, aza or thia.  
     
     
         9 . A Polymer according to  claim 7 , wherein at least one monofunctional monomer is of formula:  
       
         
           
           
               
               
           
         
       
       and mixtures thereof, and wherein p=1 or 2; M and n are as defined above, X comprises a halogen or CF 3  and R′ comprises a monovalent organic radical comprising from 1 to 12 carbon atoms, optionally fluorinated partially or entirely, and optionally substituted with one or more oxa, aza, thia, or dioathia.  
     
     
         10 . A process for the preparation of 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 plasticized homogeneously with the solvent.  
     
     
         11 . A process according to  claim 10 , wherein the monomers or mixtures of monomers are polymerized in the form of an emulsion in non-miscible solvents.  
     
     
         12 . A process according to  claim 10 , wherein the solvent comprises water, a lower aliphatic alcohol, acetone, methylethylketone, cyclic ketones, ethyl and propyl carbonates, γ-butyrolactone, glymes, N-alkylpyrolidone, tetraalkylsulfamide, dichloromethane, N-alkylimidazole, fluorinated hydrocarbons, and mixtures thereof.  
     
     
         13 . A process according to  claim 10 , wherein the polymerization radical initiator is added to the solution of monomers.  
     
     
         14 . A process according to  claim 13 , wherein the initiator is activated thermally or with an actinic radiation.  
     
     
         15 . A process according to  claim 14 , wherein the initiator is a peroxide or an azo compound.  
     
     
         16 . A process according to  claim 10 , wherein a reinforcing agent is added to the solution before the polymerization.  
     
     
         17 . A process according to  claim 10 , wherein at least one functional monomer is added.  
     
     
         18 . A process according to  claim 17 , wherein the monomer is of formula [T-SO 3 ] − M +  or [T-SO 2 —Y—SO 2 —W] − M +  wherein T, Y, M +  are as defined above, and W is a monovalent organic radical alkyl, alkenyl, aryl, arylalkyl, alkylaryl of 1 to 12 carbon atoms optionally bearing one or more substituents oxa, aza or thia.  
     
     
         19 . An electrochemical cell comprising a membrane made of a polymer obtained from the process according to  claim 10 , as a solid electrolyte.  
     
     
         20 . A cell according to  claim 19 , comprising fuel cell, a water electrolyser, an alkali-chloride cell, a salt or acid recording electrochemical cell, or an ozone producing cell.  
     
     
         21 . A cell according to  claim 19 , wherein at least one electrode is in contact with the membrane.  
     
     
         22 . The use of a polymer according to  claim 6  in an alkali-chloride electrolysis process, as a separator in an electrochemical preparation of inorganic and organic compounds, as a separator between an aqueous and an organic phase, or as a catalyst for Diels-Alder additions, Friedel-Craft reactions, aldol condensations, cationic polymerizations, esterifications, and acetal formations.