Water dispersible polypyrroles made with polymeric acid colloids for electronics applications
View Patent ↗Compositions are provided comprising aqueous dispersions of at least one polypyrrole and at least one colloid-forming polymeric acid. The colloid-forming polymeric acid may be fluorinated. The new compositions are useful in electronic devices including organic electronic devices such as organic light emitting diode displays, memory storage, electromagnetic shielding, electrochromic displays, and thin film transistors, field effect resistance devices.
1. A composition comprising a stable colloid particle containing composition comprising a continuous liquid aqueous medium having dispersed therein a polypyrrole and at least one colloid-forming polymeric acid, wherein the composition does not re-disperse in an aqueous medium after it has been dried.
2. A composition according to claim 1 , wherein said polypyrrole has Formula I below
where in Formula I:
R 1 is independently selected so as to be the same or different at each occurrence and is selected from hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylhio, 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, 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
R 2 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, amidosulfonate, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, and urethane, and may be a homopolymer or co-polymer.
3. A composition according to claim 2 , wherein R 1 is the same or different at each occurrence and is independently selected from hydrogen, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, urethane, epoxy, silane, siloxane, and alkyl substituted with one or more of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane, or siloxane moieties.
4. A composition according to claim 2 , wherein R 2 is selected from hydrogen, alkyl, and alkyl substituted with one or more of sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, cyano, hydroxyl, epoxy, silane, or siloxane moieties.
5. A composition according to claim 2 , wherein R 1 and R 2 are hydrogen.
6. A composition according to claim 2 , wherein both R 1 together form a 6- or 7-membered alicyclic ring, which is further substituted with a group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, and urethane.
7. A composition according to claim 2 , wherein both R 1 together form —O—(CHY) m —O—, where m is 2 or 3, and Y is the same or different at each occurrence and is selected from hydrogen, alkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, amidosulfonate, ether sulfonate, and urethane.
8. A composition according to claim 1 , wherein said colloid-forming polymeric acid is selected from polymeric sulfonic acids, polymeric carboxylic acids, polymeric acrylic acids, polymeric phosphoric acids, polymeric phosphonic acids, and mixtures thereof.
9. A composition according to claim 1 , wherein said polymeric acid is a fluorinated polymeric sulfonic acid.
10. A composition according to claim 9 , wherein said polymeric sulfonic acid is a perfluoroalkylenesulfonic acid.
11. The composition of claim 1 , wherein the composition further comprises at least one selected from a conductive polymer, metal particles, graphite fibers, graphite particles, carbon nanotubes, carbon nanoparticles, metal nanowires, organic conductive inks, organic conductive pastes, inorganic conductive inks, inorganic conductive pastes, charge transport materials, semiconductive inorganic oxide nano-particles, insulating inorganic oxide nano-particles, piezoelectric oxide nano-particles, piezoelectric polymers, pyrroelectric oxide nano-particles, pyrroelectric polymers, ferroelectric oxide nano-particles, ferroelectric polymers, dispersing agents, crosslinking agents and combinations thereof.
12. The composition of claim 1 , wherein the composition has a pH of 1 to 8.
13. The composition of claim 1 , wherein the colloid-forming polymeric acid includes a highly fluorinated carbon backbone and side chains represented by the formula
—(O—CF 2 CFR f ) a —O—CF 2 CFR′ f SO 3 X
wherein R f and R′ f are independently selected from F, Cl or a perfluorinated alkyl group having 1 to 10 carbon atoms, a=0, 1 or 2, and X is H.
14. An organic electronic device having at least one active layer made from a stable colloid particle containing composition comprising a continuous liquid aqueous medium having dispersed therein a polypyrrole and at least one colloid-forming polymeric acid, wherein the layer does not re-disperse in an aqueous medium after it has been formed.
15. The device of claim 14 , wherein said polypyrrole has Formula I below:
where in Formula I:
R 1 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, 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
R 2 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, amidosulfonate, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, and urethane, and may be a homopolymer or co-polymer;
and,
wherein said polymeric acid is a fluorinated polymeric sulfonic acid.