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1. (WO2007002681) ELECTRICALLY CONDUCTIVE POLYMER COMPOSITIONS
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CLAIMS
What is claimed is:
1. An electrically conductive polymer composition comprising:
at least one electrically conductive copolymer; and
at least one fluorinated acid polymer.
2. An electrically conductive polymer composition of claim 1 wherein each copolymer comprises more than one independently substituted or unsubstituted monomer selected from thiophenes, pyrroles, anilines, fused polycyclic heteroaromatics, and polycyclic heteroramatics.

3. An electrically conductive polymer composition of claim 2 wherein the thiophenes have structure represented by formulas selected from Formula I and Formula Ia:


wherein:
R1 is independently selected so as to be the same or
different at each occurrence and is selected from
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 R1 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



wherein:
R7 is the same or different at each occurrence and is selected from 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 R7 is not hydrogen, and
m is 2 or 3.
4. An electrically conductive polymer composition of claim 2 wherein the pyrroles have structure represented by Formula II:



wherein:
R1 is independently selected so as to be the same or different at
each occurrence and is selected from 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, amidosulfonate, ether carboxylate,
ether sulfonate, ester sulfonate, and urethane; or both R1 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
R2 is independently selected so as to be the same or different at
each occurrence and is selected from hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, epoxy,
silane, siloxane, alcohol, benzyl, carboxylate, ether, ether
carboxylate, ether sulfonate, ester sulfonate, and urethane.
5. An electrically conductive polymer composition of claim 2 wherein the anilines have structure represented by formulas selected from

Formula III, Formula IVa, and Formula IVb:


wherein:
a is 0 or an integer from 1 to 4;
b is an integer from 1 to 5, with the proviso that a + b = 5; and
R1 is independently selected so as to be the same or different at
each occurrence and is selected from 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 R1 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;



where a, b and R1 are as defined above.
6. An electrically conductive polymer composition of claim 2 wherein the fused polycyclic heteroaromatics have structure represented by formulas selected from Formula V, and Formulas Va - Vg:



wherein:
Q is S or NR6;
R6 is hydrogen or alkyl;
R8, R9, R10, and R11 are independently selected so as to be the
same or different at each occurrence and are selected from
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, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; and
at least one of R8 and R9, R9 and R10, and R10 and R11 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; and





wherein:
Q is S or NH; and T is the same or different at each occurrence and is selected from
S, NR6, O, SiR62, Se1 and PR6;
R6 is hydrogen or alkyl.
7. An electrically conductive polymer composition of claim 2 wherein the polycyclic heteroaromatics have structure represented by Formula Vl:



wherein:
Q is S or NR6;
T is selected from S, NR6, O, SiR62, Se, and PR6;
E is selected from alkenylene, arylene, and heteroarylene;
R6 is hydrogen or alkyl;
R12 is the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, aikanoyl, alkythio, aryloxy,
alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino,
dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl,
arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid,
phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, ester sulfonate, and urethane; or two R12 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.

8. An electrically conductive polymer composition of claim 1 wherein each fluorinated acid polymer comprises one or more
independently substituted or unsubstituted monomers selected from styrene sulfonic acids or sulfonated ether sulfones, trifluorostyrene sulfonates, sulfonimides, perfluoroalkyl sulfonate ethers, fused polycyclic fluorinated acids, and perfluoroalkyl sulfonic acid ethers.
9. An electrically conductive polymer composition of claim 8 wherein the styrene sulfonic acids or sulfonated ether sulfones have structure represented by Formula VII:



where:
b is an integer from 1 to 5,
R13 is OH or NHR14, and
R14 is alky], fluoroalkyl, sulfonylalkyl, or sulfonylfluoroalkyl.
10. An electrically conductive polymer composition of claim 8 wherein the trifluorostyrene sulfonates have structure represented by Formula VIII:


where:
W is selected from (CF2Jq1 O(CF2)q, S(CF2)q, (CF2)qO(CF2)r, and

SO2(CF2)q,
b is independently an integer from 1 to 5,
R13 is OH or NHR14, and
R14 is alkyl, fluoroalkyl, sulfonylalkyl, or sulfonylfluoroalkyl.

In one embodiment, the monomer containing W equal to S(CF2)q is polymerized then oxidized to give the polymer containing W equal to

11. An electrically conductive polymer composition of claim 8 wherein the sulfonimides have structure represented by Formula IX:

(IX)


where:
Rf is selected from fluorinated alkylene, fluorinated heteroalkylene, fluorinated arylene, or fluorinated heteroarylene;
Rg is selected from fluorinated alkylene, fluorinated heteroalkylene, fluorinated arylene, fluorinated heteroarylene, arylene, or
heteroarylene; and
n is at least 4.
12. An electrically conductive polymer composition of claim 8 wherein the perfluoroalkyl sulfonate ethers have structure represented by Formula Xl:


where:
R16 is a fluorinated alkyl or a fluorinated aryl group;
a, b, c, d, and e are each independently O or an integer from 1 to 4; and
n is at least 4.

13. An electrically conductive polymer composition of claim 8 wherein the fused polycyclic fluorinated acids have structure represented by formulas selected from Formula XlI and Formulas XIIa - XIIe:

R 17


wherein d is 0, 1 , or 2;
R17 to R20 are independently H, halogen, alkyl or alkoxy of 1 to 10 carbon atoms, Y, C(Rf1XRf1JOR21, R4Y or OR4Y;
Y is COE2, SO2 E2, or sulfonimide;
R21 is hydrogen or an acid-labile protecting group;
Rf1 is the same or different at each occurrence and is a fluoroalkyl group of 1 to 10 carbon atoms, or taken together are (CF2)e
where e is 2 to 10;
R4 is an alkylene group;
E2 is OH, halogen, or OR7; and
R5 is an alkyl group;
with the proviso that at least one of R17 to R20 is Y, R4Y or OR4Y. R4, R5, and R17 to R20 may optionally be substituted by halogen or ether oxygen; and



(XIIa) (XIIb)



(XIIc) (XIId)



(XIIe)

wherein R21 is a group capable of forming or rearranging to a tertiary cation, more typically an alkyl group of 1 to 20 carbon atoms, and most typically t-gbutyl.
14. An electrically conductive polymer composition of claim 8 wherein the perfluoroalkyl sulfonic acid ethers have structure represented by Formula XV:
— (CF2CF2)j(CH2CQ12)k(CQ22 CQ2)-

Og-[CF(Rf2)CF2-Oh]rCF2CF2SO3H

(XV) where j ≥ O1 k ≥ 0 and 4 < (j + k) ≤ 199, Q1 and Q2 are F or H, Rf2 is F or a perfluoroalkyl radical having 1-10 carbon atoms either unsubstituted or substituted by one or more ether oxygen atoms, h=0 or 1 , i=0 to 3, g=0 or 1 , and E4 is H or an alkali metal.
15. An electrically conductive polymer composition of claim 1 wherein the copolymer comprises two or more conductive precursor monomers.
16. An electrically conductive polymer composition of claim 1 wherein the copolymer comprises at least one conductive copolymer and at least one non-conductive copolymer.
17. An electrically conductive polymer composition of claim 2 wherein the pyrrole monomer is unsubstituted.
18. An electrically conductive polymer composition of claim 5 wherein the aniline monomer represented by Formula IVa or IVb is unsubstituted.
19. An electrically conductive polymer composition of claim 6 wherein the monomer represented by Formulas Vd, Ve, or Vf is a thienothiophene.
20. An electrically conductive polymer composition of claim 9 wherein the monomer represented by Formula VII is selected from SFS and SFSl.
21. An electrically conductive polymer composition of claim 1 wherein the fluorinated acid polymer comprises siloxane sulfonic acid pendant groups.
22. An electrically conductive polymer composition of claim 21 wherein fluorinated acid polymer comprises a polymeric backbone having pendant groups of the general formula:
-OaSi(OH)b-aR223-bR23RfSO3H
wherein:
a is from 1 to b;
b is from 1 to 3;
R22 is a non-hydrolyzable group independently selected from the group consisting of alkyl, aryl, and arylalkyl;

R23 is a bidentate alkylene radical, which may be substituted by one or more ether oxygen atoms, with the proviso that R23 has at least two carbon atoms linearly disposed between Si and Rf; and
Rf is a perfluoralkylene radical, which may be substituted by one or more ether oxygen atoms.
23. An electrically conductive polymer composition of claim 1 wherein the fluorinated acid polymer is a colloid-forming polymeric acid.

24. An electrically conductive polymer composition of claim 23 wherein the colloid-forming polymeric acid is an FSA polymer.
25. An electrically conductive polymer composition of claim 1 wherein the fluorinated acid polymer component forms a film that is organic solvent wettable.
26. An electrically conductive polymer composition of claim 1 wherein the fluorinated acid polymer component forms a film that is organic solvent non-wettable.
27. An electrically conductive polymer composition of claim 1 comprising a buffer.
28. An organic electronic device comprising an electrically conductive polymer composition of claim 1.
29. A method for producing an electrically conductive polymer composition, comprising forming a combination of water, at least two precursor monomers, at least one fluorinated acid polymer, and an oxidizing agent, in any order.
30. A method of claim 29 wherein at least a portion of the fluorinated acid polymer is present when the conductive monomers are added or when the oxidizing agent is added.
31. A method for producing an electronic device comprising forming a compbination of water, at least two precursor monomers, at least one fluorinated acid polymer, and an oxidizing agent, in any order.

32. A method of claim 31 wherein at least a portion of the fluorinated acid polymer is present when the conductive monomers are added or when the oxidizing agent is added.

RR