Fluorosulfonyl group-containing monomer and its polymer, and sulfonic acid group-containing polymer

Abstract

To provide a fluorosulfonyl group-containing monomer having a high polymerization reactivity and plural fluorosulfonyl groups. Further, to provide a fluorosulfonyl group-containing polymer and a sulfonic acid group-containing polymer, obtained by using the monomer. A perfluoro(2-methylene-1,3-dioxolane) derivative which is represented by the following formula (3) and which has two fluorosulfonyl groups, and its production process and its synthetic intermediate. A fluorosulfonyl group-containing polymer having monomer units represented by the following formula (3U) obtained by polymerizing the compound (3) by itself or with a comonomer, and a sulfonic acid group-containing polymer having the following units (5U) obtained by hydrolyzing a fluorosulfonyl group of the polymer. In the following formulae, each of R f1 and R f2 which are independent of each other, is a C 1-8 perfluoroalkylene group which may have an etheric oxygen atom between carbon atoms.

1 . A compound represented by the following formula (3): 
       
         
           
           
               
               
           
         
       
       wherein each of R f1  and R f2  which are independent of each other, is a C 1-8  perfluoroalkylene group which may have an etheric oxygen atom between carbon atoms. 
     
     
         2 . The compound according to  claim 1 , wherein each of —R f1 —SO 2 F and R f2 —SO 2 F is a perfluorinated 2-fluorosulfonyl ethoxy group-substituted alkylene group (the alkylene group has 1 to 3 carbon atoms). 
     
     
         3 . A process for producing a compound represented by the following formula (3), which comprises heat-decomposing a compound represented by the following formula (2); 
       
         
           
           
               
               
           
         
       
       wherein each of R f1  and R f2  which are independent of each other, is a C 1-8  perfluoroalkylene group which may have an etheric oxygen atom between carbon atoms. 
     
     
         4 . The process according to  claim 3 , wherein each of —R f1 —SO 2 F and —R f2 —SO 2 F is a perfluorinated 2-fluorosulfonyl ethoxy group-substituted alkylene group (the alkylene group has 1 to 3 carbon atoms). 
     
     
         5 . The process according to  claim 3 , wherein the compound represented by the above formula (2) is produced from a compound represented by the following formula (1) through (a) a step of epoxidation, (b) a step of forming a dioxolane ring and (c) a step of fluorination; 
       
         
           
           
               
               
           
         
       
       wherein each of R 1  and R 2  which are independent of each other, is a C 1-8  alkylene group which may have an etheric oxygen atom between carbon atoms and of which some or all of hydrogen atoms may be substituted by fluorine atoms. 
     
     
         6 . The process according to  claim 5 , wherein each of —R 1 —SO 2 F and —R 2 —SO 2 F is a 2-fluorosulfonyl-tetrafluoroethoxy group-substituted alkylene group (the alkylene group has 1 to 3 carbon atoms). 
     
     
         7 . A compound represented by the following formula (2): 
       
         
           
           
               
               
           
         
       
       wherein each of R f1  and R f2  which are independent of each other, is a C 1-8  perfluoroalkylene group which may have an etheric oxygen atom between carbon atoms. 
     
     
         8 . The compound according to  claim 7 , wherein each of —R f1 —SO 2 F and R f2 —SO 2 F is a perfluorinated 2-fluorosulfonyl ethoxy group-substituted alkylene group (the alkylene group has 1 to 3 carbon atoms). 
     
     
         9 . A process for producing a fluorosulfonyl group-containing polymer, which comprises polymerizing at least one compound represented by the following formula (3), or at least one such a compound and at least one polymerizable monomer copolymerizable with such a compound: 
       
         
           
           
               
               
           
         
       
       wherein each of R f1  and R f2  which are independent of each other, is a C 1-8  perfluoroalkylene group which may have an etheric oxygen atom between carbon atoms. 
     
     
         10 . A fluorosulfonyl group-containing polymer comprising at least one type of monomer units represented by the following formula (3U), or at least one type of such monomer units and at least one type of other monomer units: 
       
         
           
           
               
               
           
         
       
       wherein each of R f1  and R f2  which are independent of each other, is a C 1-8  perfluoroalkylene group which may have an etheric oxygen atom between carbon atoms. 
     
     
         11 . The fluorosulfonyl group-containing polymer according to  claim 10 , which has a molecular weight of from 5×10 3  to 5×10 6 , and which, when containing said other monomer units, contains from 0.1 to 99.9 mol % of monomer units represented by the formula (3U). 
     
     
         12 . A process for producing a polymer containing sulfonate groups or sulfonic acid groups, which comprises subjecting the fluorosulfonyl group in the fluorosulfonyl group-containing polymer according to  claim 10  to an alkali hydrolysis, or to such an alkali hydrolysis, followed by an acid treatment. 
     
     
         13 . A sulfonic acid group-containing polymer containing at least one type of units represented by the following formula (5U), or at least one type of such units and at least one type of other units; 
       
         
           
           
               
               
           
         
       
       wherein each of R f1  and R f2  which are independent of each other, is a C 1-8  perfluoroalkylene group which may have an etheric oxygen atom between carbon atoms. 
     
     
         14 . The sulfonic acid group-containing polymer according to  claim 13 , which has a molecular weight of from 5×10 3  to 5×10 6 , and which, when containing other units, contains from 0.1 to 99.9 mol % of units represented by the formula (5U). 
     
     
         15 . An electrolyte material for polymer electrolyte fuel cells, which comprises the sulfonic acid group-containing polymer according to  claim 13 .