Electrically conductive polymer compositions

Abstract

The present invention relates to electrically conductive polymer compositions, and their use in organic electronic devices. The electrically conductive polymer compositions include (i) an intrinsically conductive polymer having at least one monomer unit which is a pyridine-fused heteroaromatic and (ii) a fluorinated acid polymer.

1 . A polymer composition comprising:
 at least one intrinsically conductive polymer having at least one monomer unit comprising a pyridine-fused heteroaromatic; and   at least one fluorinated acid polymer.   
     
     
         2 . The composition of  claim 1 , wherein the conductive polymer is made from at least one monomer having Formula I or Formula II: 
       
         
           
           
               
               
           
         
         wherein: 
         R 1  through R 3  are independently selected so as to be the same or different at each occurrence and are hydrogen or a substituent group selected from the group consisting of alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ether sulfonic acid, ether sulfonimide, ester sulfonate, and urethane; or adjacent R groups together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms, wherein any of the substituent groups may be fluorinated; 
         Q is NR′, S, Se or Te; and 
         R′ is selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. 
       
     
     
         3 . The composition of  claim 1 , wherein the fluorinated acid polymer has a fluorinated olefin backbone and pendant groups selected from the group consisting of fluorinated ether sulfonate, fluorinated ester sulfonate, fluorinated ether sulfonimide, and combinations thereof. 
     
     
         4 . The composition of  claim 3 , wherein the sulfonimide has Formula IX: 
       
         
           
           
               
               
           
         
         where: 
         R f  is selected from fluorinated alkylene, fluorinated heteroalkylene, fluorinated arylene, and fluorinated heteroarylene; and 
         n is at least 4. 
       
     
     
         5 . The composition of  claim 1 , wherein the fluorinated acid polymer comprises a fluorinated polymer backbone and a side chain having Formula X: 
       
         
           
           
               
               
           
         
         where: 
         R 15  is a fluorinated alkylene group or a fluorinated heteroalkylene group; 
         R 16  is a fluorinated alkyl or a fluorinated aryl group; and 
         a is 0 or an integer from 1 to 4. 
       
     
     
         6 . The composition of  claim 1 , wherein the fluorinated acid polymer is selected from the group consisting of a copolymer of 1,1-difluoroethylene and 2-(2,2-difluoro-2-(trifluoromethyl)allyloxy)-1,1,2,2-tetrafluoroethanesulfonic acid; a copolymer of ethylene and 2-(2-(1,2,2-trifluorovinyloxy)-1,1,2,3,3,3-hexafluoropropoxy)-1,1,2,2-tetrafluoroethanesulfonic acid; and combinations thereof. 
     
     
         7 . The composition of  claim 1 , wherein the fluorinated acid polymer is a homopolymer or copolymer of monomers having Formula VII: 
       
         
           
           
               
               
           
         
         where: 
         b is an integer from 1 to 5, 
         R 13  is OH or NHR 14 , and 
         R 14  is alkyl, fluoroalkyl, sulfonylalkyl, or sulfonylfluoroalkyl. 
       
     
     
         8 . The composition of  claim 7 , wherein the polymer or copolymer is derived from at least one monomer SFS or SFSI: 
       
         
           
           
               
               
           
         
         wherein the polymer can be converted to the acid form following polymerization. 
       
     
     
         9 . The composition of  claim 1 , wherein the fluorinated acid polymer is a homopolymer or copolymer derived from one or more monomers having Formula VIII: 
       
         
           
           
               
               
           
         
         where: 
         W is selected from (CF 2 ) b , O(CF 2 ) b , S(CF 2 ) b , (CF 2 ) b O(CF 2 ) b , 
         b is independently an integer from 1 to 5, 
         R 13  is OH or NHR 14 , and 
         R 14  is alkyl, fluoroalkyl, sulfonylalkyl, or sulfonylfluoroalkyl. 
       
     
     
         10 . The composition of  claim 1 , wherein the fluorinated acid polymer has Formula XI: 
       
         
           
           
               
               
           
         
         where: 
         R 16  is a fluorinated alkyl or a fluorinated aryl group; 
         a, b, c, d, and e are each independently 0 or an integer from 1 to 3; and 
         n is at least 4. 
       
     
     
         11 . The composition of  claim 1 , wherein the fluorinated acid polymer has Formula XII: 
       
         
           
           
               
               
           
         
         wherein d is 0, 1, or 2; 
         R 17  to R 20  are independently H, halogen, alkyl or alkoxy of 1 to 10 carbon atoms, Y, C(R f ″)(R f ″)OR 21 , R 4 Y or OR 4 Y; 
         Y is COE 2 , SO 2  E 2 , or sulfonimide; 
         R 21  is hydrogen or an acid-labile protecting group; 
         R f ″ is the same or different at each occurrence and is a fluoroalkyl group of 1 to 10 carbon atoms, or taken together are (CF 2 ) e  where e is 2 to 10; 
         R 4  is an alkylene group; 
         E 2  is OH, halogen, or OR 5 ; and 
         R 5  is an alkyl group; 
         with the proviso that at least one of R 17  to R 20  is Y, R 4 Y or OR 4 Y. 
         R 4 , R 5 , and R 17  to R 20  may optionally be substituted by halogen or ether oxygen. 
       
     
     
         12 . The composition of  claim 11 , wherein the fluorinated acid polymer has at least one monomer unit having Formula XIIa: 
       
         
           
           
               
               
           
         
         R 17  to R 20  are independently H, halogen, alkyl or alkoxy of 1 to 10 carbon atoms, Y, C(R f ′)(R f ′)OR 21 , R 4 Y or OR 4 Y; 
         Y is COE 2 , SO 2  E 2 , or sulfonimide; 
         R 21  is hydrogen or an acid-labile protecting group; 
         R f ′ is the same or different at each occurrence and is a fluoroalkyl group of 1 to 10 carbon atoms, or taken together are (CF 2 ) e  where e is 2 to 10; 
         R 4  is an alkylene group; 
         E 2  is OH, halogen, or OR 5 ; and 
         R 5  is an alkyl group; 
         with the proviso that at least one of R 17  to R 20  is Y, R 4 Y or OR 4 Y. 
         R 4 , R 5 , and R 17  to R 20  may optionally be substituted by halogen or ether oxygen. 
       
     
     
         13 . An electronic device comprising at least one buffer layer comprising the polymer composition of  claim 1 . 
     
     
         14 . An intrinsically conductive polymer made from at least one monomer having Formula I or Formula II: 
       
         
           
           
               
               
           
         
         wherein: 
         R 1  through R 3  are independently selected so as to be the same or different at each occurrence and are hydrogen or a substituent group selected from the group consisting of alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ether sulfonic acid, ether sulfonimide, ester sulfonate, and urethane; or adjacent R groups together may form an alkylene or alkenylene chain completing a 3, 4, 5, 6, or 7-membered aromatic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms, wherein any of the substituent groups may be fluorinated; 
         Q is NR′, S, Se or Te; and 
         R′ is selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane.