Highly branched perfluoroolefins, super-stable perfluoroalkyl radicals and production methods thereof

Abstract

The present invention is to provide a method for producing a highly branched perfluoroolefin conveniently in a high yield, a novel highly branched perfluoroolefin, a method for producing a super-stable perfluoroalkyl radical and a novel super-stable perfluoroalkyl radical. The present invention is a production method of a perfluoroolefin which comprises reacting a hexafluoropropene trimer with a trialkylperfluoroalkylsilane in an aprotic polar solvent using a fluoride ion as a catalyst.

1 . A highly branched perfluoroolefin represented by the following general formula (1):  
       [(CF 3 ) 2 cf][(CF 3 ) 2 CY]C═C(CF 3 )Z   (1)  
       in the formula, Y and Z are the same or different and each represents F or Rf, Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms, provided that Y and Z are not simultaneously F.  
     
     
         2 . The highly branched perfluoroolefin according to  claim 1 , 
 wherein Y represents Rf.    
     
     
         3 . The highly branched perfluoroolefin according to  claim 2 , 
 which is perfluoro(2,4,4-trimethyl-3-isopropyl-2-pentene) or perfluoro(4,4-dimethyl-3-isopropyl-2-pentene).    
     
     
         4 . The highly branched perfluoroolefin according to  claim 1 , 
 which is perfluoro(2,4-dimethyl-3-isopropyl-2-pentene).    
     
     
         5 . A production method of a perfluoroolefin for producing the highly branched perfluoroolefin according to  claim 1 , 
 which comprises reacting a hexafluoropropene trimer with a trialkylperfluoroalkylsilane represented by the following general formula (2):                           in the formula, Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms, R 1 , R 2  and R 3  are the same or different and each represents an alkyl group having 1 to 3 carbon atoms,    in an aprotic polar solvent using a fluoride ion as a catalyst.    
     
     
         6 . The production method of the perfluoroolefin according to  claim 5 , 
 wherein the trialkylperfluoroalkylsilane is trifluoromethyltrimethylsilane.    
     
     
         7 . The production method of the perfluoroolefin according to  claim 6 , 
 wherein the aprotic polar solvent is 1,3-dimethyl-2-imidazolidinone and    wherein a highly branched perfluoroolefin (A) represented by the following general formula (3):    [(CF 3 ) 2 CF] 2 C═C(CF 3 )Rf   (3)     in the formula, Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms,    is obtained selectively.    
     
     
         8 . The production method of the perfluoroolefin according to  claim 7 , 
 wherein the highly branched perfluoroolefin, (A) is obtained at a yield of 60% by weight or higher.    
     
     
         9 . The production method of the perfluoroolefin according to  claim 7 , 
 wherein the highly branched perfluoroolefin (A) is perfluoro(2,4-dimethyl-3-isopropyl-2-pentene).    
     
     
         10 . A production method of a super-stable perfluoroalkyl radical 
 which comprises producing a super-stable perfluoroalkyl radical represented by the following general formula (1R):    [(CF 3 ) 2 CF][(CF 3 ) 2 CY]Ra—CF(CF 3 )Z   (1R)     in the formula, Ra represents a carbon atom having one unpaired electron, Y and Z are the same or different and each represents F or Rf, and Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms, provided that Y and Z are not simultaneously F,    by fluorinating the highly branched perfluoroolefin according to  claim 1 .    
     
     
         11 . The production method of the super-stable perfluoroalkyl radical according to  claim 10 , 
 wherein the fluorination is conducted using a fluorine gas.    
     
     
         12 . The production method of the super-stable perfluoroalkyl radical according to  claim 11 , 
 wherein the fluorine gas is a pure one.    
     
     
         13 . The production method of the super-stable perfluoroalkyl radical according to  claim 10 , 
 wherein the highly branched perfluoroolefin is one obtained by reacting a hexafluoropropene trimer with a trialkylperfluoroalkylsilane represented by the following general formula (2):                           in the formula, Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms, R 1 , R 2  and R 3  are the same or different and each represents an alkyl group having 1 to 3 carbon atoms,    in an aprotic polar solvent using a fluoride ion as a catalyst.    
     
     
         14 . The production method of the super-stable perfluoroalkyl radical according to  claim 10 , 
 wherein Y and Z are the same or different and each represents F or a trifluoromethyl group, provided that Y and Z are not simultaneously F.    
     
     
         15 . The production method of the super-stable perfluoroalkyl radical according to  claim 10 , 
 wherein the highly branched perfluoroolefin is perfluoro(2,4-dimethyl-3-isopropyl-2-pentene), perfluoro(2,4,4-trimethyl-3-isopropyl-2-pentene) or perfluoro(4,4-dimethyl-3-isopropyl-2-pentene).    
     
     
         16 . A production method of a reduced-carbon super-stable perfluoroalkyl radical 
 which comprises producing a super-stable perfluoroalkyl radical (AR) represented by the following general formula (3R):    [(CF 3 ) 2 CF] 2 Ra—CF(CF 3 )Rf   (3R)     in the formula, Ra represents a carbon atom having one unpaired electron and Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms,    by fluorinating a highly branched perfluoroolefin (B) represented by the following general formula (4):    [(CF 3 ) 2 CF][(CF 3 ) 2 CRf]C═C(CF 3 )Rf   (4)    in the formula, each Rf is the same or different from each other and is defined as described above.    
     
     
         17 . The production method of the reduced-carbon super-stable perfluoroalkyl radical according to  claim 16 , 
 wherein Rf represents a trifluoromethyl group.    
     
     
         18 . A super-stable perfluoroalkyl radical (BR) represented by the following general formula (4R):  
       [(CF 3 ) 2 CF][(CF 3 ) 2 CRf]Ra—CF(CF 3 )Rf   (4R)   in the formula, Ra represents a carbon atom having one unpaired electron and each Rf is the same or different from each other and represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms.    
     
     
         19 . The super-stable perfluoroalkyl radical according to  claim 18 , 
 which is perfluoro(2,4,4-trimethyl-3-isopropyl-3-pentyl).    
     
     
         20 . A super-stable perfluoroalkyl radical (CR) represented by the following general formula (5R):  
       [(CF 3 ) 2 CF][(CF 3 ) 2 CRf]Ra—CF 2 (CF 3 )   (5R)   in the formula, Ra represents a carbon atom having one unpaired electron and Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms.    
     
     
         21 . The super-stable perfluoroalkyl radical according to  claim 20 , 
 which is perfluoro(4,4-dimethyl-3-isopropyl-3-pentyl).