Electrically conductive polymer compositions
View Patent ↗Electrically conducting polymer compositions are provided. The compositions comprise homopolymers and copolymers of polythiophene, polypyrrole, polyaniline, and polycyclic heteroaromatics, and combinations of those, in admixture with an organic solvent wettable fluorinated acid polymer. The acid polymers are fluorinated or highly fluorinated and have acidic groups including carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof. The compositions may be used in organic electronic devices (OLEDs).
1. A polymer composition comprising at least one doped electrically conductive polythiophene polymer in admixture with at least one organic solvent wettable fluorinated acid polymer wherein said solvent wettable fluorinated acid polymer forms a film which is wettable by phenylhexane with a contact angle no greater than 40°.
2. The composition of claim 1 , wherein the polythiophene has Formula I:
wherein:
R 1 is independently selected so as to be the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, 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, ester sulfonate, and urethane; or both R 1 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 or oxygen atoms, and n is at least about 4.
3. The composition of claim 1 , wherein the polythiophene has Formula I(a):
wherein:
R 7 is the same or different at each occurrence and is selected from the group consisting of hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amidosulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane, with the proviso that at least one R 7 is not hydrogen,
m is 2 or 3, and
n is at least about 4.
4. The composition of claim 1 , wherein the polymeric fused polycyclic heteroaromatic is derived from a monomer having Formula V:
wherein:
Q is S;
R 8 , R 9 , R 10 , and R 11 are independently selected so as to be the same or different at each occurrence and are selected from the group consisting of hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkythio, 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, ester sulfonate, and urethane; and
at least one of R 8 and R 9 , R 9 and R 10 , and R 10 and R 11 together form an alkenylene chain completing a 5 or 6-membered aromatic ring, which ring may optionally include one or more divalent nitrogen, sulfur or oxygen atoms.
5. The composition of claim 1 , wherein the electrically conductive polymer is selected from the group consisting of poly(3,4-ethylenedioxythiophene), poly(thieno(2,3-b)thiophene), poly(thieno(3,2-b)thiophene), and poly(thieno(3,4-b)thiophene).
6. The composition of claim 5 , wherein the dopant is a polymeric sulfonic acid.
7. The composition of claim 5 , wherein the contact angle is no greater than 35°.
8. The composition of claim 1 , wherein the doped electrically conductive polymer comprises a non-fluorinated polymeric acid dopant.
9. The composition of claim 1 , wherein the organic-solvent wettable fluorinated acid polymer comprises an acidic group selected from the group consisting of carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof.
10. The composition of claim 1 , wherein the organic-solvent wettable fluorinated acid polymer comprises a backbone selected from the group consisting of polyolefins, polyacrylates, polymethacrylates, polyimides, polyamides, polyaramids, polyacrylamides, and copolymers thereof.
11. The composition of claim 1 , wherein the organic-wettable fluorinated acid polymer comprises fluorinated side chains selected from the group consisting of alkyl groups, alkoxy groups, amido groups, ether groups, and combinations thereof.
12. The composition of claim 1 , wherein the organic-solvent wettable fluorinated acid polymer comprises a fluorinated olefin backbone and pendant groups selected from the group consisting of fluorinated ether sulfonate groups and fluorinated ether sulfonimide groups.
13. The composition of claim 1 , wherein the organic-solvent wettable 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.
14. The composition of claim 1 , wherein the organic-solvent wettable fluorinated acid polymer comprises a fluorinated and partially sulfonated arylene ether sulfone.
15. The composition of claim 1 , wherein the organic-solvent wettable fluorinated acid polymer is derived from at least one monomer having a formula selected from Formula VII
where:
q is an integer from 1 to 5,
R 13 is OH or NHR 14 , and
R 14 is alkyl, fluoroalkyl, sulfonylalkyl, or sulfonylfluoroalkyl;
and Formula VIII
where:
W is selected from the group consisting of (CF 2 ) q , O(CF 2 ) q , S(CF 2 ) q , (CF 2 ) q O(CF 2 ) r ,
q and r are independently an integer from 1 to 5,
R 13 is OH or NHR 14 , and
R 14 is alkyl, fluoroalkyl, sulfonylalkyl, or sulfonylfluoroalkyl.
16. The composition of claim 1 , wherein the organic-solvent wettable fluorinated acid polymer has Formula IX
where:
R f is selected from the group consisting of fluorinated alkylene, fluorinated heteroalkylene, fluorinated arylene, and fluorinated heteroarylene; and
n is at least 20.
17. The composition of claim 1 , wherein the organic-wettable 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
p is 0 or an integer from 1 to 4.
18. The composition of claim 1 , wherein the organic-solvent wettable 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.
19. An aqueous dispersion of polymer composition comprising at least one electrically conductive polythiophene polymer blended with at least one organic solvent wettable fluorinated acid polymer, wherein the composition has a pH between 1.5 and 4 wherein said solvent wettable fluorinated acid polymer forms a film which is wettable by phenylhexane with a contact angle no greater than 40°.
20. The dispersion of claim 19 , wherein the pH is between 2 and 3.