Conjugated polymers from substituted 3,4-propylenedioxythiophene, compositions, method of making, and use thereof

Abstract

Polymers and copolymers having units derived from substituted 3,4-propylenedioxythiophene are disclosed. Also provided are methods of making and using the same.

1 . A substituted 3,4-propylenedioxythiophene according to the structure (I): 
       
         
           
           
               
               
           
         
       
       wherein each instance of R 1 , R 2 , R 3 , and R 4  independently is hydrogen; optionally substituted C 3 -C 20  alkyl, C 1 -C 20  haloalkyl, aryl, C 1 -C 20  alkoxy, C 1 -C 20  haloalkoxy, aryloxy, —C 1 -C 10  alkyl-O—C 1 -C 10  alkyl, —C 1 -C 10  alkyl-O-aryl, or —C 1 -C 10  alkyl-aryl; or hydroxyl;
 with the proviso that at least one of a R 1  or a R 2  group is not hydrogen, and when R 1  or R 2  is an alkyl, at least two of the R 1  and R 2  groups are not hydrogen; 
 wherein the C 3 -C 20  alkyl, C 1 -C 20  haloalkyl, aryl, C 1 -C 20  alkoxy, C 1 -C 20  haloalkoxy, aryloxy, —C 1 -C 10  alkyl-O—C 1 -C 10  alkyl, —C 1 -C 10  alkyl-O-aryl, or —C 1 -C 10  alkyl-aryl group each may be optionally substituted with one or more of C 1 -C 20  alkyl; aryl; halogen; hydroxyl; —N—(R 7 ) 2  wherein each R 7  is independently hydrogen or C 1 -C 6  alkyl; cyano; nitro; —COOH; —S(═O)C 0 -C 10  alkyl; or —S(═O) 2 C 0 -C 10  alkyl. 
 
     
     
         2 . The substituted 3,4-propylenedioxythiophene of  claim 1 , wherein each instance of R 1  and R 2  independently is hydrogen; optionally substituted C 3 -C 10  alkyl, C 1 -C 10  haloalkyl, aryl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkoxy, aryloxy, —C 1 -C 5  alkyl-O—C 1 -C 5  alkyl, —C 1 -C 5  alkyl-O-aryl, or —C 1 -C 5  alkyl-aryl; or hydroxyl; and R 3  and R 4  are both hydrogen. 
     
     
         3 . The substituted 3,4-propylenedioxythiophene of  claim 1 , wherein each instance of R 1  and R 2  independently is hydrogen; or optionally substituted C 3 -C 5  alkyl, C 1 -C 5  haloalkyl, aryl, C 1 -C 5  alkoxy, C 1 -C 5  haloalkoxy, aryloxy, —C 1 -C 3  alkyl-O—C 1 -C 3  alkyl, —C 1 -C 3  alkyl-O-aryl, or —C 1 -C 3  alkyl-aryl; or hydroxyl; and R 3  and R 4  are both hydrogen. 
     
     
         4 . The substituted 3,4-propylenedioxythiophene of  claim 1 , wherein each instance of R 1  and R 2  independently is hydrogen; or optionally substituted C 3 -C 20  alkyl, C 1 -C 20  haloalkyl, aryl, or —C 1 -C 10  alkyl-aryl; and R 3  and R 4  are both hydrogen. 
     
     
         5 . The substituted 3,4-propylenedioxythiophene of  claim 1 , wherein each instance of R 1  and R 2  independently is hydrogen; or optionally substituted C 3 -C 20  alkyl, C 1 -C 20  haloalkyl, aryl, or —C 1 -C 10  alkyl-aryl; and R 3  and R 4  are both hydrogen, with the proviso that at least two of the R 1  or R 2  groups are not hydrogen. 
     
     
         6 . The substituted 3,4-propylenedioxythiophene of  claim 1 , wherein each instance of R 1  and R 2  independently is hydrogen; or optionally substituted C 3 -C 10  alkyl, or —C 1 -C 10  alkyl-aryl; and R 3  and R 4  are both hydrogen, with the proviso that at least two of the R 1  or R 2  groups are not hydrogen. 
     
     
         7 . The substituted 3,4-propylenedioxythiophene of  claim 1 , wherein at least two of the R 1  and R 2  groups are not hydrogen while the remaining two are hydrogen. 
     
     
         8 . A method of preparing a substituted 3,4-propylenedioxythiophene according to the structure (I): 
       
         
           
           
               
               
           
         
       
       wherein each instance of R 1 , R 2 , R 3 , and R 4  independently is hydrogen; optionally substituted C 3 -C 20  alkyl, C 1 -C 20  haloalkyl, aryl, C 1 -C 20  alkoxy, C 1 -C 20  haloalkoxy, aryloxy, —C 1 -C 10  alkyl-O—C 1 -C 10  alkyl, —C 1 -C 10  alkyl-O-aryl, or —C 1 -C 10  alkyl-aryl; or hydroxyl; wherein the C 1 -C 20  alkyl, C 1 -C 20  haloalkyl, aryl, C 1 -C 20  alkoxy, C 1 -C 20  haloalkoxy, aryloxy, —C 1 -C 10  alkyl-O—C 1 -C 10  alkyl, —C 1 -C 10  alkyl-O-aryl, or —C 1 -C 10  alkyl-aryl group each may be optionally substituted with one or more of C 1 -C 20  alkyl; aryl; halogen; hydroxyl; —N—(R 7 ) 2  wherein each R 7  is independently hydrogen or C 1 -C 6  alkyl; cyano; nitro; —COOH; —S(═O)C 0 -C 10  alkyl; or —S(═O) 2 C 0 -C 10  alkyl;
 with the proviso that at least one of a R 1  or a R 2  group is not hydrogen, and when R 1  or R 2  is an alkyl, at least two of the R 1  and R 2  groups are not hydrogen, comprising 
 reacting a 3,4-dialkoxythiophene according to the structure 
 
       
         
           
           
               
               
           
         
         wherein R 5  is an alkyl group, 
       
       with a substituted diol according to the structure 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2 , R 3 , and R 4  are as defined above, or their appropriately protected functional group equivalents. 
       
     
     
         9 . The method of  claim 8 , wherein each instance of R 1  and R 2  independently is hydrogen; optionally substituted C 3 -C 10  alkyl, C 1 -C 10  haloalkyl, aryl, C 1 -C 10  alkoxy, C 1 -C 10  haloalkoxy, aryloxy, —C 1 -C 5  alkyl-O—C 1 -C 5  alkyl, —C 1 -C 5  alkyl-O— aryl, or —C 1 -C 5  alkyl-aryl; or hydroxyl; and R 3  and R 4  are both hydrogen. 
     
     
         10 . The method of  claim 8 , wherein each instance of R 1  and R 2  independently is hydrogen; or optionally substituted C 3 -C 5  alkyl, C 1 -C 5  haloalkyl, aryl, C 1 -C 5  alkoxy, C 1 -C 5  haloalkoxy, aryloxy, —C 1 -C 3  alkyl-O—C 1 -C 3  alkyl, —C 1 -C 3  alkyl-O-aryl, or —C 1 -C 3  alkyl-aryl; or hydroxyl; and R 3  and R 4  are both hydrogen. 
     
     
         11 . The method of  claim 8 , wherein each instance of R 1  and R 2  independently is hydrogen; or optionally substituted C 3 -C 20  alkyl, C 1 -C 20  haloalkyl, aryl, or —C 1 -C 10  alkyl-aryl; and R 3  and R 4  are both hydrogen. 
     
     
         12 . The method of  claim 8 , wherein each instance of R 1  and R 2  independently is hydrogen; or optionally substituted C 3 -C 20  alkyl, C 1 -C 20  haloalkyl, aryl, or —C 1 -C 10  alkyl-aryl; and R 3  and R 4  are both hydrogen, with the proviso that at least two of the R 1  or R 2  groups are not hydrogen. 
     
     
         13 . The method of  claim 8 , wherein each instance of R 1  and R 2  independently is hydrogen; or optionally substituted C 3 -C 10  alkyl, or —C 1 -C 10  alkyl-aryl; and R 3  and R 4  are both hydrogen, with the proviso that at least two of the R 1  or R 2  groups are not hydrogen. 
     
     
         14 . The method of  claim 8 , wherein at least two of the R 1  and R 2  groups are not hydrogen while the remaining two are hydrogen. 
     
     
         15 . The method of  claim 8 , wherein R 5  is C 1 -C 4  alkyl.