Fluorinated bis(phthalic anhydride) and method for producing the same

Abstract

It is an object of the present invention to provide fluorinated bis(phthalic anhydride) which has less coloration and higher solubility in comparison with conventional compounds, and a method for producing the same. Further, it is also an object of the present invention to provide a method for producing a fluorinated bis(phthalonitrile) compound, which is an intermediate raw material compound of the method for producing the fluorinated bis(phthalic anhydride), and a polyamic acid and a polyimide, which are produced from the fluorinated bis(phthalic anhydride). A fluorinated bis(phthalic anhydride) of the present invention is the fluorinated bis(phthalic anhydride) represented by the following formula (I 1 ), wherein its specific surface area is 3.0 m 2 /g or larger. It is also characterized in that its molar absorption coefficient is 0.6 L/mol·cm or less at a wavelength of 360 nm. [wherein, m and n independently represent integers of 1 to 3, and Z 1 represents a single bond group or a bivalent organic group.]

1 . A fluorinated bis(phthalic anhydride) represented by the following formula (I 1 ), wherein its specific surface area is 3.0 m 2 /g or larger.  
       
         
           
           
               
               
           
         
       
       [wherein, m and n independently represent integers of 1 to 3, and Z 1  represents a single bond group or a bivalent organic group.] 
     
     
         2 . A fluorinated bis(phthalic anhydride) represented by the following formula (I 1 ), wherein its molar absorption coefficient is 0.6 L/mol·cm or less at a wavelength of 360 nm.  
       
         
           
           
               
               
           
         
       
       [wherein, m and n independently represent integers of 1 to 3, and Z 1  represents a single bond group or a bivalent organic group.] 
     
     
         3 . A method for producing the fluorinated bis(phthalic anhydride) (I 1 ) from a fluorinated bis(phthalic acid) compound (II 1 ) as shown in the following formulae, wherein fluorinated bis(phthalic acid) compound (II 1 ) is dehydrated by using an aliphatic carboxylic anhydride in an organic solvent.  
       
         
           
           
               
               
           
         
       
       [wherein, m and n independently represent integers of 1 to 3, and Z 1  represents a single bond group or a bivalent organic group.] 
     
     
         4 . The method of production according to  claim 3 , wherein an aromatic hydrocarbon and/or an aliphatic hydrocarbon is used as said organic solvent.  
     
     
         5 . The method of production according to  claim 3 , wherein an intended compound is crystallized by adding a poor solvent after the completion of a reaction.  
     
     
         6 . The method of production according to  claim 4 , wherein an intended compound is crystallized by adding a poor solvent after the completion of a reaction.  
     
     
         7 . A method for producing a fluorinated bis(phthalonitrile) compound (V), 
 wherein a fluorinated phthalonitrile derivative (III) and a compound (IV) are condensed as shown in the following formula:                          [wherein, p represents an integer of 2 to 4, Z 2  represents a bivalent organic group, and m and n independently represent integers of 1 to 3.];    the fluorinated phthalonitrile derivative (III) was used in excess over the compound (IV); and    after the condensation, the fluorinated bis(phthalonitrile) compound (V) is separated from the remaining fluorinated phthalonitrile derivative (III) through the use of the difference between solubility thereof in an organic solvent.    
     
     
         8 . A method for producing a fluorinated bis(phthalic anhydride) (I 2 ), 
 wherein a fluorinated phthalonitrile derivative (III) and a compound (IV) are condensed to form the fluorinated bis(phthalonitrile) compound (V), this compound (V) is hydrolyzed to obtain a fluorinated bis(phthalic acid) (II 2 ), and this acid (II 2 ) is dehydrated to produce the fluorinated bis(phthalic anhydride) (I 2 ) as shown in the following formula:                          [wherein, p represents an integer of 2 to 4, Z 2  represents a bivalent organic group, and m and n independently represent integers of 1 to 3.];    the fluorinated phthalonitrile derivative (III) was used in excess over the compound (IV);    after the condensation, the fluorinated bis(phthalonitrile) compound (V) is separated from the remaining fluorinated phthalonitrile derivative (III) through the use of the difference between solubility thereof in an organic solvent; and    the fluorinated bis(phthalic acid) compound (II 2 ) is dehydrated using an aliphatic carboxylic anhydride in an organic solvent.    
     
     
         9 . A polyamic acid represented by the following formula (VII), wherein being produced using the fluorinated bis(phthalic anhydride) according to  claim 1  and a diamine compound (VI) as raw materials:  
       
         
           
           
               
               
           
         
       
       [wherein, m and n independently represent integers of 1 to 3, Z 1  represents a single bond group or a bivalent organic group, and X represents a bivalent organic group.] 
     
     
         10 . A polyamic acid represented by the following formula (VII), wherein being produced using the fluorinated bis(phthalic anhydride) according to  claim 2  and a diamine compound (VI) as raw materials.  
       
         
           
           
               
               
           
         
       
       [wherein, m and n independently represent integers of 1 to 3, Z 1 represents a single bond group or a bivalent organic group, and X represents a bivalent organic group.] 
     
     
         11 . Polyimide represented by the following formula (VIII), wherein being produced by using the polyamic acid (VII) according to  claim 9  as a raw material.  
       
         
           
           
               
               
           
         
       
       [wherein, m and n independently represent integers of 1 to 3, Z 1  represents a single bond group or a bivalent organic group, and X represents a bivalent organic group.] 
     
     
         12 . Polyimide represented by the following formula (VIII), wherein being produced by using the polyamic acid (VII) according to  claim 10  as a raw material.  
       
         
           
           
               
               
           
         
       
       [wherein, m and n independently represent integers of 1 to 3, Z 1  represents a single bond group or a bivalent organic group, and X represents a bivalent organic group.]