Terphenyl dihydroxy monomers containing fluorine and fluorinated poly(arylene ether sulfide)s

Abstract

The present invention relates to terphenyl dihydroxy monomers containing fluorine and fluorinated poly(arylene ether sulfide)s prepared by using the monomers, more particularly, terphenyl dihydroxy monomers containing both two hydroxy functional groups and fluorine and fluorinated poly(arylene ether sulfide)s prepared by an aromatic nucleophilic substitution polymerization (S N Ar) using the monomers, which are thus useful as optical materials in the field of information telecommunications.

1 . A terphenyl dihydroxy monomer containing fluorine expressed by formula 1:  
     
       
         
         
             
             
         
       
     
     wherein X is a fluorine atom or a fluoroalkyl group having 1 to 6 carbon atoms; and n represents the number of X as a substituent and is an integer of 1 to 5.  
   
   
       2 . The terphenyl dihydroxy monomer containing fluorine of  claim 1 , wherein said compound expressed by formula 1 is selected from the group consisting of 
 2′,5′-dimethoxy-4,4″-bis-trifluoromethyl-[1,1′,4′,1″]terphenyl,    4,4″-bis-trifluoromethyl-[1,1′,4′,1″]terphenyl-2′,5′-diol,    2′,5′-dimethoxy-3,5,3″,5″-tetrakis-trifluoromethyl-[1,1′,4′,1″]terphenyl,    3,5,3″,5″-tetrakis-trifluoromethyl-[1,1′,4′,1″]terphenyl-2′,5′-diol,    2,3,5,6,2″,3″,5″,6″-octafluoro-2′,5′-dimethoxy-4,4″-bis-trifluoromethyl-[1,1′,4′,1″]terphenyl, and    2,3,5,6,2″,3″,5″,6″-octafluoro-4,4″-bis-trifluoromethyl-[1,1′,4′,1″]terphenyl-2′,5′-diol.    
   
   
       3 . A process for preparing terphenyl dihydroxy monomer containing fluorine expressed by formula 1, comprising: 
 preparing 1,4-dibromo-2,5-dialkoxy benzene expressed by formula 3 by bromination of 1,4-dialkoxy benzene expressed by formula 2;    preparing 2,5-dialkoxy-1,4-benzeneboronic acid expressed by formula 4 by converting bromine (Br) of 1,4-dibromo-2,5-dialkoxy benzene expressed by formula 3 to boronic acid; and    preparing terphenyl dihydroxy monomer containing fluorine expressed by formula 1 via Suzuki cross-coupling reaction between 2,5-dialkoxy-1,4-benzeneboronic acid expressed by formula 4 and bromobenzene containing fluorine expressed by formula 5,                          wherein R′ is an alkyl group of from 1 to 6 carbon atoms; R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; X is a fluorine (F) atom or a fluoroalkyl group having 1 to 6 carbon atoms; n represents the number of X as a substituent and is an integer of 1 to 5.    
   
   
       4 . The process of  claim 3 , wherein said compound expressed by formula 1, where R is an alkyl group having 1 to 6 carbon atoms, prepared via Suzuki cross-coupling reaction further comprises a step of converting to the compound where R is a hydrogen atom through the hydrolysis using acid solution.  
   
   
       5 . A poly(arylene ether sulfide) substituted with fluorine expressed by formula 6:  
     
       
         
         
             
             
         
       
     
     wherein D is a fluorine atom or an ethynylphenoxy group, X is a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms, n represents the number of X as a substituent and is an integer of 1 to 5, and M represents the number of monomers.  
   
   
       6 . The poly(arylene ether sulfide) substituted with fluorine of  claim 5 , wherein said poly(arylene ether sulfide) substituted with fluorine is selected from the group consisting of  
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
   
   
       7 . A process for preparing poly(arylene ether sulfide) containing fluorine comprising: 
 a) preparing a polymer (D=F) expressed by formula 6a by the polycondensation of terphenyl dihydroxy monomer of formula 1 and sulfide compound of formula 7; and    b) preparing a polymer (D=—O-Z) expressed by formula 6b by reacting the polymer of formula 6a with a cross-linkable compound expressed by Z-OH,                          wherein X is a hydrogen atom, a fluorine atom, or a fluoroalkyl having 1 to 6 carbon atoms, n represents the number of X as a substituent and is an integer of 1 to 5, M represents the number of monomers, and Z is an ethynylphenyl group as a cross-linkable group.    
   
   
       8 . The process of  claim 7 , wherein said terphenyl dihydroxy monomer expressed by formula 1 is selected from the group consisting of 
 [1,1′,4′,1″]terphenyl-2′,5′-diol,    2′,5′-dimethoxy-4,4″-bis-trifluoromethyl-[1,1′,4′,1″]terphenyl; 4,4″-bis-trifluoromethyl-[1,1′,4′,1″]terphenyl-2′,5′-diol,    2′,5′-dimethoxy-3,5,3″,5″-tetrakis-trifluoromethyl-[1,1′,4′,1″]terphenyl    3,5,3″,5″-tetrakis-trifluoromethyl-[1,1′,4′,1″]terphenyl-2′,5′-diol,    2,3,5,6,2″,3″,5″,6″-octafluoro-2′,5′-dimethoxy-4,4″-bis-trifluoromethyl-[1,1′,4′,1″]terphenyl, and    2,3,5,6,2″,3″,5″,6″-octafluoro-4,4″-bis-trifluoromethyl-[1,1′,4′,1″]terphenyl-2′,5′-diol.    
   
   
       9 . The process of  claim 7 , wherein said step a) and step b) are performed in the presence of a base and an aprotic polar solvent at 100 to 200° C.