Compositions produced by solvent exchange methods and uses thereof

Abstract

Disclosed are compositions formed by a method for exchanging the water in an optionally substituted polythiophene dispersion with a specific mixture of organic solvents. The resulting compositions exhibit improved electrical conductivity, optical transparency, environmental stability, excellent adhesion to a variety of substrates and processing characteristics. Also disclosed are methods for making and using such compositions.

What is claimed is:  
     
         1 . A method for replacing water in an aqueous dispersion of an optionally substituted polythiophene cation and associated anion with one or more organic solvents, comprising: 
 heating a mixture of an aqueous dispersion of an optionally substituted polythiophene cation and associated polyanion in a vessel with one or more organic solvents, wherein the one or more organic solvents have a boiling point between from about 80° C. to about 290° C., to vaporize at least 30% of the water from said mixture.    
     
     
         2 . The method of  claim 1 , wherein the heating vaporizes greater than about 90% of the water from the mixture in said vessel.  
     
     
         3 . The method of  claim 1 , wherein an inorganic additive is added during or at the end of the heating step.  
     
     
         4 . The method of  claim 1 , wherein the heating vaporizes at least 95% of the water from the mixture in said vessel.  
     
     
         5 . The method of  claim 1 , wherein the one or more organic solvents includes lower alkyl acetamides, lower alcohols including diols and triols, pyrrolidones, lower alkyl pyrrolidones, higher alkyl pyrrolidones, lower alkyl sulfoxides, and mixtures thereof.  
     
     
         6 . The method of  claim 1 , wherein the one or more organic solvent includes a glycol or glycerin.  
     
     
         7 . The method of  claim 1 , wherein the one or more organic solvent includes dimethylsulfoxide.  
     
     
         8 . The method of  claim 1 , wherein the one or more organic solvents includes ethylene glycol, dimethylacetamide, N-methylpyrrolidone, or mixtures thereof.  
     
     
         9 . The method of  claim 1 , wherein the one or more organic solvents have a boiling point between from about 100° C. to about 250° C.  
     
     
         10 . The method of  claim 1 , wherein the one or more organic solvents is ethylene glycol by volume in the mixture from about 5% to about 95%.  
     
     
         11 . The method of  claim 1 , wherein the one or more organic solvents and the aqueous dispersion are heated in the vessel to a temperature of from between from about 100° C. to about 250° C.  
     
     
         12 . The method of  claim 1 , wherein the one or more organic solvents and aqueous dispersion are heated at a pressure of from about 5.1 mm Hg to about 5171 mm Hg in the vessel.  
     
     
         13 . The method of  claim 1 , further including the step of contacting the heated one or more organic solvents and the aqueous dispersion mixture with a flow of inert gas.  
     
     
         14 . The method of  claim 1 , further comprising subjecting the polythiophene mixture to high sheer mixing sufficient to prevent or reduce agglomeration of the mixture.  
     
     
         15 . The method of  claim 1 , wherein the optionally substituted polythiophene cation is represented by the following formula (I):  
       
         
           
           
               
               
           
         
         wherein R1 and R2 each independently represent hydrogen or a C1-C6 alkyl group, or together form an optionally substituted C1-C6 radical or cyclohexylene-1,2 radical, and n is greater than 1.  
       
     
     
         16 . The method of  claim 1 , wherein the polyanion is an anion of a polymeric carboxylic acid, a polymaleic acid, a polymeric sulphonic acid, or mixtures thereof.  
     
     
         17 . The method of  claim 1 , wherein the polyanion is polystyrene sulfonic acid (PSS).  
     
     
         18 . A method for exchanging water in an aqueous dispersion of optionally substituted polythiophene cation and associated anion with one or more organic solvents comprising: 
 contacting in a vessel an amount of one or more organic solvents, wherein the one or more organic solvents have a boiling point between from about 80° C. to about 290° C., with an aqueous dispersion of an optionally substituted polythiophene cation and associated polyanion; and    heating to a temperature sufficient to vaporize at least 30% of the water from said aqueous dispersion.    
     
     
         19 . The method of  claim 18 , wherein the contacting step further comprises adding about 1 part of the aqueous dispersion to more than about 0.1 to about 10,000,000 parts of the one or more heated organic solvent per minute.  
     
     
         20 . The method of  claim 18 , wherein the contacting removes greater than about 90% of the water from the aqueous dispersion in said vessel.  
     
     
         21 . The method of  claim 18 , wherein the contacting removes greater than about 95% of the water from the aqueous dispersion in said vessel.  
     
     
         22 . The method of  claim 18 , wherein the one or more organic solvents includes lower alkyl acetamides, lower alcohols including diols and triols, pyrrolidones, lower alkyl pyrrolidones, higher alkyl pyrrolidones, lower alkyl sulfoxides, and mixtures thereof.  
     
     
         23 . The method of  claim 18 , wherein the one or more organic solvent includes a glycol or glycerin.  
     
     
         24 . The method of  claim 18 , wherein the one or more organic solvent includes dimethylsulfoxide.  
     
     
         25 . The method of  claim 18  wherein the one or more organic solvents includes ethylene glycol, dimethylacetamide, N-methylpyrrolidone, or mixtures thereof.  
     
     
         26 . The method of  claim 18 , wherein the one or more organic solvents have a boiling point between from about 100° C. to about 250° C.  
     
     
         27 . The method of  claim 18 , wherein the one or more organic solvents and the aqueous dispersion are heated in the vessel to a temperature of from between about 100° C. to about 250° C.  
     
     
         28 . The method of  claim 18 , wherein the one or more organic solvents and aqueous dispersion are heated at a pressure of from about 5.1 mm Hg to about 5171 mm Hg in the vessel.  
     
     
         29 . The method of  claim 18 , wherein the contacting step further comprises subjecting the one or more organic solvents and aqueous dispersions to high sheer mixing sufficient to prevent to reduce agglomeration of the mixture.  
     
     
         30 . The method of  claim 18 , wherein at least one of the solvents is water soluble.  
     
     
         31 . The method of  claim 18 , wherein the one or more organic solvents includes ethylene glycol by volume in the mixture from about 5% to about 95%.  
     
     
         32 . The method of  claim 18 , wherein the one or more organic solvents is a mixture of ethylene glycol and N-methylpyrrolidone (NMP).  
     
     
         33 . The method of  claim 18 , wherein the one or more organic solvents is a mixture of ethylene glycol and NMP in a ratio of 80:20 (v/v).  
     
     
         34 . The method of  claim 18 , wherein an inorganic additive is added to the vessel.  
     
     
         35 . The method of  claim 34 , wherein the organic additive is 4-hydroxybenzene sulfonic acid.  
     
     
         36 . The method of  claim 18 , wherein between from about at least 30% (w/v) to about at least 99% (w/v) of the water is removed from the mixture as vapor.  
     
     
         37 . The method of  claim 18 , further including the step of contacting the heated solvent and aqueous dispersion with an inert gas.  
     
     
         38 . The method of  claim 18 , wherein the polyanion is an anion of a polymeric carboxylic acid, a polymaleic acid, a polymeric sulphonic acid, or mixtures thereof.  
     
     
         39 . The method of  claim 18 , wherein the polyanion is polystyrene sulfonic acid (PSS).  
     
     
         40 . The method of  claim 18 , wherein the polythiophene cation is represented by the following formula (I):  
       
         
           
           
               
               
           
         
         wherein R1 and R2 each independently represent hydrogen or a C1-C6 alkyl group, or together form an optionally substituted C1-C6 radical or a cyclohexylene-1,2 radical, and n is greater than 1.  
       
     
     
         41 . The method of  claim 40 , wherein the C1-C6 radical is an ethylene 1,2 radical.  
     
     
         42 . The method of  claim 40 , wherein n is greater than 1.  
     
     
         43 . The method of  claim 40 , wherein n is from about 5 to about 5000.  
     
     
         44 . The method of  claim 18 , wherein the polythiophene is an aqueous dispersion of about 0.5 to about 5% by weight poly-3,4-ethylene dioxythiophene.  
     
     
         45 . The method of  claim 18 , further including an additive in said vessel that is a binder.  
     
     
         46 . The method of  claim 18 , further including an additive in said vessel that is a wetting agent.  
     
     
         47 . The method of  claim 18 , further including an additive in said vessel that is an adhesion promoter.  
     
     
         48 . A method for exchanging water in an aqueous dispersion of a poly 3,4-ethylene dioxythiophene cation and associated polystyrene sulfonic acid polyanion with a solvent mixture comprising: 
 contacting one or more organic solvents, wherein one or more organic solvents have a boiling point between from about 80° C. to about 290° C., wherein the one or more solvents are heated in a vessel to a temperature of between about 100° C. to about 250° C.    with an amount of the aqueous dispersion in the vessel to form an exchange mixture; the contact at a rate sufficient to remove at least part of the water from the aqueous dispersion as vapor; and    heating said exchange mixture to further remove water from the exchange mixture.    
     
     
         49 . The method of  claim 48 , wherein the contact rate is between from about 0.1 to about 1000 mL/minute.  
     
     
         50 . The method of  claim 48 , wherein the vapor is removed from the heated exchange mixture in said vessel with a flow of an inert gas.  
     
     
         51 . The method of  claim 48 , wherein the water removal from the vessel is facilitated by an azeotroping agent.  
     
     
         52 . The method of  claim 48 , wherein from about 30% (w/v) to 99% (w/v) of the water is removed from the exchange mixture.  
     
     
         53 . The method of  claim 48 , wherein the one or more organic solvents includes lower alkyl acetamides, lower alcohols including diols and triols, pyrrolidones, lower alkyl pyrrolidones, higher alkyl pyrrolidones, lower alkyl sulfoxides, and mixtures thereof.  
     
     
         54 . The method of  claim 48 , wherein the one or more organic solvent includes a glycol or glycerin.  
     
     
         55 . The method of  claim 48 , wherein the one or more organic solvent includes dimethylsulfoxide.  
     
     
         56 . The method of  claim 48  wherein the one or more organic solvents includes ethylene glycol, dimethylacetamide, N-methylpyrrolidone, or mixtures thereof.  
     
     
         57 . The method of  claim 48 , wherein the one or more organic solvents have a boiling point between from about 100° C. to about 250° C.  
     
     
         58 . The method of  claim 48 , wherein the solvent mixture includes from about 5% to about 95% ethylene glycol by volume.  
     
     
         59 . The method of  claim 48 , wherein the solvent mixture is ethylene glycol and N-methylpyrrolidone in a ratio of 80:20 (v/v).  
     
     
         60 . The method of  claim 48 , wherein the conditions further comprise exposing the solvent mixture to a pressure from about 5.1 mm Hg to about 5171 mm Hg in the vessel.  
     
     
         61 . The method of  claim 48 , further comprises subjecting the exchange mixture to high sheer mixing.  
     
     
         62 . The method of  claim 48 , wherein the polyanion is an anion of a polymeric carboxylic acid, a polymaleic acid, a polymeric sulphonic acid, or mixtures thereof.  
     
     
         63 . The method of  claim 48 , wherein the polyanion is polystyrene sulfonic acid (PSS).  
     
     
         64 . The method of  claim 48  , wherein the aqueous dispersion contains at least one additive.  
     
     
         65 . The method of  claim 64 , wherein the additive is a binder.  
     
     
         66 . The method of  claim 64 , wherein the additive is a wetting agent.  
     
     
         67 . The method of  claim 64 , wherein the additive is an adhesion promoter.