Claims
- 1. A method for exchanging the water in an optionally substituted polythiophene/anion dispersion for a specific mixture of solvents, comprising:
a) heating a specific solvent mixture in a vessel under conditions suitable for vaporizing water, b) contacting the heated specific solvent mixture with a mixture comprising water and optionally substituted polythiophene/anion, the contact being sufficient to remove at least part of the water from the mixture as vapor; and c) optionally adding an organic or inorganic additive during or after the exchange process; and d) exchanging the water removed from the mixture with the specific solvent mixture.
- 2. The method of claim 1, wherein the method further comprises removing the water from the vessel.
- 3. The method of claim 2, wherein the water vapor removed from the mixture is a condensate or distillate.
- 4. The method of claim 2, wherein the water removal from the vessel is facilitated by an azeotroping agent.
- 5. The method of claim 4, wherein the azeotroping agent is toluene, benzene, mesitylene or one or a mixture of xylene isomers.
- 6. The method of claim 1, wherein the specific solvent mixture is comprised of a mixture of at least two organic solvents.
- 7. The method of claim 1, wherein the boiling point of at least one of the specific solvents is at least 100° C. at standard temperature and pressure (STP).
- 8. The method of claim 1, wherein the boiling point of at least one of the specific solvents is between about 100° C. to about 250° C. at standard temperature and pressure (STP).
- 9. The method of claim 1, wherein the specific solvent mixture is heated in the vessel to about 100° C.
- 10. The method of claim 1, wherein the specific solvent mixture is heated in the vessel to a temperature of between from about 100° C. to about 250° C.
- 11. The method of claim 1, wherein the conditions further comprise exposing the specific solvent mixture to a pressure from about 0.1 pounds per square inch to about 100 pounds per square inch in the vessel.
- 12. The method of claim 11, wherein the conditions further comprise exposing the specific solvent mixture to a pressure of between about 0.1 pounds per square inch to ambient pressure (14.7 pounds per square inch) in the vessel.
- 13. The method of claim 1, wherein the contacting step further comprises subjecting the polythiophene mixture to high sheer mixing sufficient to prevent or reduce agglomeration of the mixture.
- 14. The method of claim 13, wherein the high sheer mixing is provided by a homogenization or dispersion implementation.
- 15. The method of claim 1, wherein the contacting step further comprises adding about 1 part of the mixture to more than about 1 part heated specific solvent mixture per minute.
- 16. The method of claim 1, wherein the contacting step further comprises adding about 1 part of the mixture to more than about 5 to about 10,000,000 parts heated specific solvent mixture per minute.
- 17. The method of claim 1, wherein the contacting step further comprises adding the mixture to the heated specific solvent mixture as a flow stream, aerosol; or a combination thereof.
- 18. The method of claim 17, wherein the addition of the mixture is continuous.
- 19. The method of claim 17, wherein the addition of the mixture is discontinuous.
- 20. The method of claim 19, wherein the mixture added to the specific solvent mixture as a discontinuous flow stream.
- 21. The method of claim 17, wherein the mixture is added to the specific solvent mixture as drops.
- 22. The method of claim 1, wherein he contacting step further comprises dispersing the mixture along the surface of the heated specific solvent mixture.
- 23. The method of claim 22, wherein the dispersal is configured to maximize contact between the mixture and the heated specific solvent mixture.
- 24. The method of claim 1, wherein the contacting step further comprises adding the mixture below the surface of the heated specific solvent mixture.
- 25. The method of claim 1, wherein at least one of the solvents in the specific solvent mixture is soluble in water.
- 26. The method of claim 1, wherein at least one of the solvents in the specific solvent mixture is partially soluble or insoluble in water.
- 27. The method of claim 26, wherein the specific solvent mixture is comprised of any combination of at least two of ethylene glycol, dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP).
- 28. The method of claim 27, wherein the relative amount of ethylene glycol by volume in the mixture comprises from about 5% to about 95%.
- 29. The method of claim 28 wherein the specific solvent mixture is comprised of ethylene glycol and N-methylpyrrolidone (NMP).
- 30. The method of claim 29 wherein the relative amount of ethylene glycol by volume in the mixture with NMP comprises from about 5% to about 95%.
- 31. The method of claim 30 wherein the relative amount of ethylene glycol by volume in the mixture with NMP comprises 80%.
- 32. The method of claim 30 wherein the relative amount of ethylene glycol by volume in the mixture with NMP comprises 50%.
- 33. The method of claim 1, wherein an inorganic additive is added during or at the end of the solvent exchange process.
- 34. The method of claim 1, wherein an organic additive is added during or at the end of the solvent exchange process.
- 35. The method of claim 34, wherein the organic additive is 4-hydroxybenzene sulfonic acid.
- 36. The method of claim 1, wherein less than about 100% (w/v) of the water is removed from the mixture as vapor.
- 37. The method of claim 36, wherein between from about 25% (w/v) to about 100% (w/v) of the water is removed from the mixture.
- 38. The method of claim 36, wherein between from about 50% (w/v) to about 100% (w/v) of the water is removed from the mixture.
- 39. The method of claim 1, wherein between from about 1% (w/v) to about 100% (w/v) of the water is removed from the mixture.
- 40. The method of claim 1, wherein the polythiophene is represented by the following formula (I):
- 41. The method of claim 40, wherein the polythiophene is associated with at least one polyanion.
- 42. The method of claim 41, wherein the polyanion is polystyrene sulfonic acid (PSS).
- 43. The method of claim 40, wherein R1 and R2 each independently represent C1-C4 alkyl or together form a C1-C4 radical.
- 44. The method of claim 40, wherein R1 and R2 taken together form an ethylene 1,2 radical.
- 45. The method of claim 40, wherein n is less than about 10.
- 46. The method of claim 40, wherein n is less than about 5.
- 47. The method of claim 40, wherein the polythiophene is an optionally substituted poly 3,4-alkylene dioxythiophene.
- 48. The method of claim 47, wherein the polythiophene is poly 3,4-ethylene dioxythiophene.
- 49. The method of claim 1, wherein the polythiophene/anion aqueous dispersion is known commercially as Baytron®P.
- 50. The method of claim 42, wherein the optionally substituted polythiophene dispersion further comprises at least one additive.
- 51. The method of claim 50, wherein at least one of the additives is a binder.
- 52. The method of claim 50, wherein at least one of the additives is a wetting agent.
- 53. The method of claim 50, wherein at least one of the additives is an adhesion promoter.
- 54. A method for exchanging the water in an aqueous dispersion comprising poly 3,4-ethylene dioxythiophene/polystyrene sulfonic acid with a specific solvent mixture comprised of at least two of ethylene glycol, N-methylpyrrolidinone and N,N-dimethylacetamide comprising;
a) contacting the heated specific solvent mixture containing any two or all hree of ethylene glycol, N-methylpyrrolidinone and/or N,N-dimethylacetamide in a first vessel to a temperature of between from about 100° C. to about 250° C. b) contacting the heated ethylene glycol and N-methylpyrrolidone (NMP) and/or dimethylacetamide (DMAC) mixture with an amount of the aqueous dispersion comprising poly-3,4-ethylene dioxythiophene/polystyrene sulfonic acid, wherein the dispersion is added to the surface of the heated specific solvent at a rate of between from about 0.1 to about 1000 mL/minute, the contact being sufficient to remove at least part of the water from the dispersion as vapor; c) optionally adding an organic or inorganic additive during or after the exchange process; and d) exchanging the water removed from the dispersion as vapor with a specific solvent mixture containing any two or all three of ethylene glycol, N-methylpyrrolidinone and/or N,N-dimethylacetamide.
- 54. The method of claim 54, wherein the method further comprises removing the water from the vessel.
- 56. The method of claim 55, wherein the water vapor removed from the mixture is a condensate or distillate.
- 57. The method of claim 55, wherein the water removal from the vessel is facilitated by an azeotroping agent.
- 58. The method of claim 57, wherein the azeotroping agent is toluene, benzene, mesitylene, or at least one xylene isomer.
- 59. The method of claim 54, wherein the specific solvent mixture is heated in the vessel to about 100° C.
- 60. The method of claim 54, wherein the specific solvent mixture is heated in the vessel to a temperature of between from about 100° C. to about 250° C.
- 61. The method of claim 54, wherein the conditions further comprise exposing the specific solvent mixture to a pressure from about 0.1 pounds per square inch to 100 pounds per square inch in the vessel.
- 62. The method of claim 61, wherein the conditions further comprise exposing the specific solvent mixture to a pressure of between about 0.1 pounds per square inch to ambient pressure (14.7 pounds per square inch) in the vessel.
- 63. The method of claim 54, wherein the contacting step further comprises subjecting the polythiophene mixture to high sheer mixing sufficient to prevent or reduce agglomeration of the mixture.
- 64. The method of claim 63, wherein the high sheer mixing is provided by a homogenization or dispersion implementation.
- 65. The method of claim 54, wherein the contacting step further comprises adding about 1 part of the mixture to more than about 1 part heated specific solvent mixture per minute.
- 66. The method of claim 54, wherein the specific solvent mixture comprises ethylene glycol and N-methylpyrrolidinone (NMP).
- 67. The method of claim 66, wherein the relative amount of ethylene glycol by volume in the mixture with NMP comprises from about 5% to about 95%.
- 68. The method of claim 66 wherein the relative amount of ethylene glycol by volume in the mixture with NMP comprises 80%.
- 69. The method of claim 66 wherein the relative amount of ethylene glycol by volume in the mixture with NMP comprises 50%.
- 70. The method of claim 54, wherein the ratio of the amount of the specific solvent mixture to the amount of the aqueous dispersion is more than one.
- 71. The method of claim 70, wherein the ratio is between from about 1 to about 10,000,000 or more.
- 72. The method of claim 70, wherein the ratio is between from about 1.5 to about 10.
- 73. The method of claim 54, wherein the method further comprises contacting the heated specific solvent mixture with at least one non-reactive gas to facilitate removal of the water from the mixture.
- 74. The method of claim 73, wherein the gas is nitrogen, air, a noble gas; or a mixture thereof.
- 75. The method of claim 74, wherein the gas is pre-heated to about the temperature of the heated solvent.
- 76. The method of claim 54, wherein less than about 100% (w/v) of the water is removed from the aqueous mixture.
- 77. The method of claim 76, wherein between from about 25% (w/v) to about 99% (w/v) of the water is removed from the aqueous mixture.
- 78. The method of claim 76, wherein between from about 50% (w/v) to about 99% (w/v) of the water is removed from the mixture.
- 79. The method of claim 76, wherein between from about 1% (w/v) to about 99% (w/v) of the water is removed from the mixture.
- 80. The method of claim 54, wherein about 100% (w/v) of the water is removed from the mixture.
- 81. The method of claim 54, wherein the poly 3,4-ethylene dioxythiophene/polystyrene sulfonic acid is provided as a colloidal water dispersion.
- 82. The method of claim 54, wherein the poly 3,4-ethylene dioxythiophene/polystyrene sulfonic acid colloidal water dispersion is commercially available as Baytron® P.
- 83. The method of claim 82, wherein the colloidal aqueous dispersion contains at least one additive.
- 84. The method of claim 83, wherein the additive is a binder.
- 85. The method of claim 83, wherein the additive is a wetting agent.
- 86. The method of claim 83, wherein the additive is an adhesion promoter.
- 87. A composition produced by any one of the methods of claim 1 or claim 54.
- 88. A composition according to claim 87 comprising a poly-3,4-alkylene dioxythiophene; and between from about 25% (w/v) to about 100% (w/v) of a mixture of ethylene glycol with either N-methylpyrrolidone (NMP) or dimethylacetamide (DMAC).
- 89. The composition of claim 88, wherein the poly-3,4-alkylene dioxythiophene is associated with at least one polyanion.
- 90. The composition of claim 89, wherein the polyanion is polystyrene sulfonic acid (PSS).
- 91. The composition of claim 90, wherein the specific solvent mixture is comprised of ethylene glycol and N-methylpyrrolidinone.
- 92. The composition of claim 91, wherein the amount of ethylene glycol in the mixture ranges from about 5% to about 95% by volume.
- 93. The composition of claim 92, wherein the amount of ethylene glycol in the specific solvent mixture is about 80% by volume.
- 94. The composition of claim 93, wherein the amount of ethylene glycol in the specific solvent mixture is about 50% by volume.
- 95. The composition of claim 90, wherein the optionally substituted poly-3,4-alkylene dioxythiophene is poly-3,4-ethylene dioxythiophene commercially available as Baytron® P.
- 96. The composition of claim 90 further comprising at least one additive.
- 97. The composition of claim 96, wherein the additive is a binder.
- 98. The composition of claim 96, wherein the additive is ferric toluene sulfonic acid (Baytron® C).
- 99. The composition of claim 96, wherein the additive is a wetting agent.
- 100. The composition of claim 96, wherein the additive is an adhesion promoter.
- 101. The composition of claim 96, wherein the additive is 4-hydroxybenzene sulfonic acid.
- 102. A composition derived from the method of claim 1, wherein the composition has at least an order of magnitude higher conductivity than the corresponding unexchanged polythiophene mixture.
- 103. The composition derived from the method of claim 1, wherein the composition comprises a converted (solvent exchanged) polydioxythiophene and the unexchanged polythiophene mixture is Baytron® P.
- 104. A conductive coating composition derived from the method of claim 1, wherein the coating has a surface resistance of between from about 10 to about 1012 ohm/square.
- 105. A composition derived from the method of claim 54, wherein the composition has at least an order of magnitude higher conductivity than the corresponding unexchanged polythiophene mixture.
- 106. The composition derived from the method of claim 54, wherein the composition comprises a converted (solvent exchanged) polydioxythiophene and the unexchanged polythiophene mixture is Baytron® P.
- 107. A conductive coating composition derived from the method of claim 54, wherein the coating has a surface resistance of between from about 10 to about 1012 ohm/square.
- 108. A conductive coating composition derived from the method of claim 54, wherein the coating has a surface resistance of between from about 10 to about 1012 ohm/square.
- 109. The coating material derived from the method of claim 1 having between from about 1 mg/m2 to about 500 mg/m2 of the composition in the layer.
- 110. The coating material derived from the method of claim 54 having between from about 1 mg/m2 to about 500 mg/m2 of the composition in the layer.
- 111. The coating of claim 1 in which the layer has an optical density of between from about 0.0001 to about 0.05 at between from about 300 nm to about 700 nm.
- 112. The coating material of claim 54, wherein the layer has a light transmission of between from about 10% to about 99% as measured by a BYK Gardner Haze-gard plus machine.
- 113. A conducting polymer coating derived from the composition of claim 90, wherein the coating exhibits a charge carrier mobility of greater than 0.1° Cm2/V-S.
- 114. A conducting polymer coating derived from the composition of claim 90, wherein the coating exhibits a charge carrier mobility of greater than 1 Cm2/V-S.
- 115. A conducting polymer coating derived from the composition of claim 90, wherein the coating is prepared by employing non-vacuum coating processes, wherein the coating exhibits a charge carrier mobility of greater than 1 Cm2/V-S.
- 116. A conducting polymer coating derived from the composition of claim 90, wherein the coating exhibits a charge carrier mobility of greater than 10 Cm2/V-S, wherein the charge carrier mobility is measured by the combination of van der Pauw and Hall effect methods.
- 117. A conductive coating comprising the composition of claim 90 on the surface of an organic, inorganic, ceramic or hybrid organic/inorganic/ceramic substrate.
- 118. The conductive coating of claim 117, wherein the substrate is a polymer film.
- 119. The conductive coating of claim 118, wherein the substrate is polyester or polycarbonate or polyimide.
- 120. The conductive coating of claim 119, where the substrate is poly ethylene terephthalate.
- 121. The conductive coating of claim 119, where the substrate is a polyimide known as TOR-NC.
- 122. A coated object derived from the product obtained from the method of claim 1.
- 123. The conductive coating of claim 117, wherein the object is in the form of a sheet, film, foil, foam, fiber, thread, molding, laminate, adhesive, irregular shaped particle, nanoparticle, carbon, inorganic or ceramic nanotube, or combination thereof.
- 124. A conductive coating derived from the method of claim 1 or claim 54, wherein the coating has a surface resistance equal to or less than about 2500 ohm/square while having an optical transparency of greater than 85% while having good adhesion to glass or plastic while having a thickness less than about 250 nanometers.
- 125. A conductive coating of claim 124 wherein the coating is on flexible or rigid glass.
- 126. A conductive coating of claim 124, wherein the coating is on polyethylene terephthalate.
- 127. A conductive coating of claim 31 wherein the coating is on polyethylene terephathalate and wherein the coating has a surface resistance equal to or less than about 2500 ohm/square while having an optical transparency of greater than 85% while having good adhesion to glass or plastic while having a thickness less than about 250 nanometers
- 128. A conducting polymer coating derived from the composition of claim 31, wherein the coating exhibits a charge carrier mobility of greater than 1 Cm2/V-S.
- 129. A conducting polymer coating derived from the composition of claim 127, wherein the coating exhibits a charge carrier mobility of greater than 4 Cm2/V-S.
- 130. A conducting polymer coating derived from the composition of claim 31 prepared by employing non-vacuum coating processes, wherein the coating exhibits a charge carrier mobility of greater than 4 Cm2/V-S.
- 131. A conducting polymer coating exhibiting a charge carrier mobility of greater than 4 Cm2/V-S, wherein the charge carrier mobility is measured by the combination of van der Pauw and Hall effect methods.
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a Continuation-In-Part of U.S. patent application Ser. No. 09/999,171 filed on Nov. 30, 2001 which application claims benefit to U.S. Provisional Application No. 60/298,174 as filed on Jun. 13, 2001, and U.S. Provisional Application No. 60/269,606 as filed on Feb. 16, 2001. The disclosures of the U.S. Ser. Nos. 09/999,171, 60/298,174 and 60/269,606 applications are each incorporated herein by reference.
Provisional Applications (2)
|
Number |
Date |
Country |
|
60298174 |
Jun 2001 |
US |
|
60269606 |
Feb 2001 |
US |
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
09991171 |
Nov 2001 |
US |
Child |
10167043 |
Jun 2002 |
US |