Process for producing a fluorine atom-containing sulfonyl fluoride compound

Abstract

The present invention provides a process whereby fluorine atom-containing sulfonyl fluoride compound(s) useful as e.g. materials for ion-exchange membranes, can be produced efficiently and at low cost without structural limitations while solving the difficulties in production. Namely, the present invention provides a process which comprises reacting XSO 2 R A -E 1 (1) with R B -E 2 (2) to form XSO 2 R 4 -E-R B (3), then reacting (3) with fluorine in a liquid phase to form FSO 2 R AF -E F -R BF (4), and further, decomposing the compound to obtain FSO 2 R AF -E Fl (5), wherein R A is a bivalent organic group, E 1 is a monovalent reactive group, R B is a monovalent organic group, E 2 is a monovalent reactive group which is reactive with E 1 , E is a bivalent connecting group formed by the reaction of E 1 with E 2 , R AF is a bivalent organic group formed by the fluorination of R A , etc., R BF is the same group as R B , etc., E F1 is a bivalent connecting group formed by the fluorination of E, etc., E F1 is a monovalent group formed by the decomposition of E F , and X is a halogen atom.

1. A process for producing a fluorine atom-containing sulfonyl fluoride compound, which comprises reacting a compound of the following formula (1) with a compound of the following formula (2) to form a compound of the formula (3), then, reacting the compound of the formula (3) with fluorine in a liquid phase to form a compound of the following formula (4), and further, decomposing the compound of the formula (4) to obtain a compound of the following formula (5):
   XSO 2 R A -E 1    (1)  
   R B -E 2    (2)  
   XSO 2 R A -E-R B    (3)  
   FSO 2 R AF -E F -R BF    (4)  
   FSO 2 R AF -E F1    (5)  
 wherein R A  is a bivalent organic group, E 1  is a monovalent reactive group, R B  is a monovalent organic group, E 2  is a monovalent reactive group which is reactive with E 1 , E is a bivalent connecting group formed by the reaction of E 1 , with E 2 , R AF  is the same group as R A , or a bivalent organic group formed by the fluorination of R A , R BF  is the same group as R B , or a monovalent organic group formed by the fluorination of R B , E F  is the same group as E, or a bivalent connecting group formed by the fluorination of E, E F1  is a monovalent group formed by the decomposition of E F , and X is a halogen atom, provided that at least one of R A , R B  and E is a group which can be fluorinated, and at least one of R AF , R BF  and E F  is a group formed by the fluorination of R A , R B  and E, respectively.  
 
     
     
       2. The process for producing a fluorine atom-containing sulfonyl fluoride compound according to  claim 1 , wherein X is a fluorine atom. 
     
     
       3. The process for-producing a fluorine atom-containing sulfonyl fluoride compound according to  claim 1 , wherein the fluorine content in the compound of the formula (3) is at least 30 mass %. 
     
     
       4. The process for producing a fluorine atom-containing sulfonyl fluoride compound according to  claim 1 , wherein the molecular weight of the compound of the formula (3) is from 200 to 1,000. 
     
     
       5. The process for producing a fluorine atom-containing sulfonyl fluoride compound according to  claim 1 , wherein R AF  is a bivalent organic group selected from the group consisting of a perfluoro bivalent saturated hydrocarbon group, a perfluoro(partially halogeno bivalent saturated hydrocarbon) group, a perfluoro(hetero atom-containing bivalent saturated hydrocarbon) group, and a perfluoro(partially halogeno(hetero atom-containing bivalent saturated hydrocarbon)) group, and R BF  is a monovalent organic group selected from the group consisting of a perfluoro monovalent saturated hydrocarbon group, a perfluoro(partially halogeno monovalent saturated hydrocarbon) group, a perfluoro(hetero atom-containing monovalent saturated hydrocarbon) group, and a perfluoro(partially halogeno(hetero atom-containing monovalent saturated hydrocarbon)) group. 
     
     
       6. The process for producing a fluorine atom-containing sulfonyl fluoride compounds according to  claim 1 , wherein the compound of the formula (4) is decomposed to obtain not only the compound of the formula (5), but also a compound of the following formula (6):
   R BF -B F2    (6)  
 wherein E F2  is a monovalent group formed by the decomposition of E F , which may be the same as or different from E F1 , and R BF  is as defined above.  
 
     
     
       7. The process for producing a fluorine atom-containing sulfonyl fluoride compound according to  claim 1 , wherein the compound of the formula (1) is a compound of the following formula (1a), the compound of the formula (2) is a compound of the following formula (2a), the compound of the formula (3) is a compound of the following formula (3a), the compound of the formula (4) is a compound of the following formula (4a), and the compound of the formula (5) is a compound of the following formula (5a):
   XSO 2 R A —CH 2 OH   (1a)  
   R B —COY   (2a)  
   XSO 2 R A —CH 2 OCO—R B    (3a)  
   FSO 2 R AF —CF 2 OCO—R BF    (4a)  
   FSO 2 R AF —COF   (5a)  
 wherein Y is a halogen atom which is the same as or different from X, and R A , R B , R AF  and R BF  are as defined above.  
 
     
     
       8. The process for producing a fluorine atom-containing sulfonyl fluoride compound according to  claim 7 , wherein the compound of the formula (4a) is decomposed to obtain not only the compound of the formula (5a), but also a compound of the following formula (6a):
   R BF —COF   (6a)  
 wherein R BF  is as defined above.  
 
     
     
       9. The process for producing a fluorine atom-containing sulfonyl fluoride compound according to  claim 8 , wherein the compound of the formula (2a) has the same structure as the compound of the formula (6a), and at least a part of the compound of the formula (6a) obtained from the reaction product obtained by the decomposition of the compound of the formula (4a), is used as at least a part of the compound of the formula (2a) to react with the compound of the formula (1a), to continuously obtain the compound of the formula (5a). 
     
     
       10. A process for producing compound of the following formula (   5 a ) , which comprises reacting a compound of the following formula  (   3 a )  with fluorine in a liquid phase to form a compound of the following formula (   4 a ) , and further, decomposing the compound of the following formula  (   4 a )  to obtain a compound of the following formula  (   5 a ):   XSO 2   R   A   —CH   2   OC ( O ) —R   BF    ( 3 a)      FSO 2   R   AF   —CF   2   OC ( O ) —R   BF    ( 4 a)      FSO 2   R   AF   —COF    ( 5 a)    
       wherein
   R   A    is a saturated hydrocarbon group, a partially halogeno bivalent saturated hydrocarbon group, a hetero atom - containing bivalent saturated hydrocarbon group, and a partially halogeno ( hetero atom - containing bivalent saturated hydrocarbon )  group,        R   AF    is a bivalent organic group selected from the group consisting of a perfluoro bivalent saturated hydrocarbon group, a perfluoro ( partially halogeno bivalent saturated hydrocarbon )  group, a perfluoro ( hetero atom - containing bivalent saturated hydrocarbon )  group, and a perfluoro ( partially halogeno ( hetero atom - containing bivalent saturated hydrocarbon )  group,        R   BF    is a monovalent organic group selected from the group consisting of a perfluoro monovalent saturated hydrocarbon group, a perfluoro ( partially halogeno monovalent saturated hydrocarbon )  group, a perfluoro ( hetero atom - containing monovalent saturated hydrocarbon )  group, and a perfluoro ( partially halogeno ( hetero atom - containing monovalent saturated hydrocarbon )  group, and        X is Cl or F, and        wherein said hetero atom - containing group, monovalent or divalent, is group containing a hetero atom selected from the group consisting of oxygen atom, nitrogen atom, and sulfur atom, or said hetero atom - containing group, monovalent or divalent, is —C—C ( ═O )— C— or —C—SO   2   —C—.     
     
     
       11. The process for producing compound according to  claim 10 , wherein
   R   A    is C   1-10    alkylene group or C   1-20    etheric oxygen atom - containing alkylene group and        R   AF    is C   1-10    perfluoro ( alkylene group )  or C   1-20    perfluoro ( etheric oxygen atom - containing alkylene group ).   
     
     
       12. The process for producing compound according to  claim 10 , wherein
   R   BF    is a perfluoro monovalent saturated hydrocarbon group or a perfluoro ( hetero atom - containing monovalent saturated hydrocarbon )  group.     
     
     
       13. The process for producing compound according to  claim 10 ,
   wherein R   BF    is a C   1-20    perfluoro ( hetero atom - containing monovalent saturated hydrocarbon )  group.     
     
     
       14. The process for producing compound according to  claim 10 , wherein the compound (   3 a )  has a molecular weight of  200  to  1000 .   
     
     
       15. The process for producing compound according to  claim 10 , wherein X is a fluorine atom. 
     
     
       16. The process for producing compound according to  claim 10 , wherein the compound (   3 a )  has fluorine content of at least  30  mass  %. 
     
     
       17. The process for producing compound according to  claim 10 , wherein the compound (   3 a )  has fluorine content of at least  30  to  86  mass  %.