Novel polythiophene dispersions

Abstract

A process for the preparation of dispersions or solutions comprising polythiophene + An − ion complexes in anhydrous or low-water-content organic solvents, characterized in that at least one water-miscible organic solvent or a water-miscible solvent mixture is added to an aqueous dispersion or solution comprising optionally substituted polythiophenes, all or some of the water is removed, and the resultant dispersion or solution is, if desired, diluted with organic solvents.

1 . A process for preparing a dispersion or a solution containing an optionally substituted polythiophene in an organic solvent, comprising: 
 a) adding a water-miscible organic solvent or a water-miscible solvent mixture to an aqueous dispersion or solution comprising optionally substituted polythiophenes; and    b) removing at least some of the water from the mixture resulting from step a), and thereby forming the dispersion of the solution.    
     
     
         2 . The process according to  claim 1 , wherein the process further comprises diluting the dispersion or the solution resulting from the process with an organic solvent or a mixture of organic solvents subsequent to step b).  
     
     
         3 - 10 . (canceled)  
     
     
         11 . A dispersion or a solution comprising: 
 (a) a polythiophene + An −  ion complex, wherein the polythiophene +  is a polymer comprising recurring units represented by formula (I).                          at least some of which are positively charged and wherein,    Y is —(CH 2 ) m —CR 1 R 2 (CH 2 ) n — or an optionally substituted 1,2-C 3 -C 8 -cycloalkylene radical, and    R 1  and R 2 , independently of one another, are hydrogen, hydroxymethyl, an optionally substituted C 1 -C 20 -alkyl radical or an optionally substituted C 6 -C 14 -aryl, and    m and n are identical or different and are an integer from 0 to 3, and further wherein,    An −  is an anion of an organic polyacid; and    (b) a solvent selected from the group consisting of low-water-content solvent and anhydrous organic solvent.    
     
     
         12 . The dispersion or the solution according to  claim 11 , wherein the dispersion or the solution has an inorganic salt content that is less than about 40% of the amount originally employed for the preparation of the An − polythiophene + .  
     
     
         13 . The dispersion or the solution according to  claim 11 , wherein the dispersion or the solution has a water content ranging from 0 to about 5% by weight.  
     
     
         14 . A dispersion or a solution comprising: 
 (a) a polythiophene + An −  ion complex, wherein the polythiophene + An −  is a polymer comprising recurring units represented by formula (II)                          wherein at least some of the thiophene rings carry a positive charge, and wherein,    Z is —(CH 2 ) m —CR 3 R 4 (CH 2 ) n —,    R 3  is hydrogen or —(CH 2 ) s —O—(CH 2 ) p —SO 3   − M + ,    R 4  is —(CH 2 ) s —O—(CH 2 ) p —SO 3   − M + ,    m and n are an integer from 0 to 3,    M +  is a cation,    s is an integer from 0 to 10, and    p is an integer from 1 to 18; and    (b) a solvent selected from the group consisting of low-water-content solvent and anhydrous organic solvent.    
     
     
         15 . The dispersion or the solution according to  claim 14 , wherein the dispersion or the solution has an inorganic salt content that is less than about 40% of the amount originally employed for the preparation of the An − polythiophene + .  
     
     
         16 . The dispersion of  claim 14 , wherein the solution or the dispersion has a water content is from 0 to about 5% by weight.  
     
     
         17 . A process for providing a substrate with conductivity comprising applying a dispersion or a solution to a substrate, 
 wherein the dispersion or the solution comprises a polythiophene + An −  ion complex in organic solvents, and the solution or the dispersion being prepared by a process comprising,    a) adding a water-miscible organic solvent or a water-miscible organic solvent mixture to an aqueous dispersion or a solution of a polythiophene + An −  ion complex,    wherein polythiophene +  is a polymer comprising recurring units selected from the group consisting of recurring units represented by the following formula (I) and formula (II)                          at least some of which are positively charged and for formula (I),    Y is —(CH 2 ) m —CR 1 R 2 (CH 2 ) n — or an optionally substituted 1,2-C 3 -C 8 -cycloalkylene radical, and    R 1  and R 2 , independently of one another, are hydrogen, hydroxymethyl, an optionally substituted C 1 -C 20 -alkyl radical or an optionally substituted C 6 -C 14 -aryl radical, and    m and n are identical or different and are an integer from 0 to 3, and further wherein, and    An −  is an anion of an organic polyacid, and for formula (II)                          at least some of the thiophene rings carry a positive charge, and    Z is —(CH 2 ) m —CR 3 R 4 (CH 2 ) n —,    R 3  is hydrogen or —(CH 2 ) s —O—(CH 2 ) p —SO 3   − M + ,    R 4  is —(CH 2 ) s —O—(CH 2 ) p —SO 3   − M + ,    m and n are an integer from 0 to 3,    M +  is a cation,    s is an integer from 0 to 10, and    p is an integer from 1 to 18, and    b) removing water from the mixture resulting in step a).    
     
     
         18 . A process for antistatic finishing of substrates comprising applying a dispersion or a solution comprising a polythiophene + An −  ion complex to a substrate, 
 wherein the dispersion or the solution contains a polythiophene + An −  ion complex in an organic solvent, and the solution or the dispersion being prepared by a process comprising,    a) adding a water-miscible organic solvent or a water-miscible organic solvent mixture to an aqueous dispersion or a solution of a polythiophene + An −  ion complex,    wherein polythiophene +  is a polymer comprising recurring units selected from the group consisting of recurring units represented by the following formula (I) and formula (II),                          at least some of which are positively charged and in which for formula (I),    Y is —(CH 2 ) m —CR 1 R 2 (CH 2 ) n — or an optionally substituted 1,2-C 3 -C 8 -cycloalkylene radical, and    R 1  and R 2 , independently of one another, are hydrogen, 
 hydroxymethyl, an optionally substituted C 1 -C 20 -alkyl radical or an optionally substituted C 6 -C 14 -aryl radical, and  
   m and n are identical or different and are an integer from 0 to 3, and further wherein,    An −  is an anion of an organic polyacid, and for formula (II),                          at least some of the thiophene rings carry a positive charges and    Z is —(CH 2 ) m —CR 3 R 4 (CH 2 ) n —,    R 3  is hydrogen or —(CH 2 ) s —O—(CH 2 ) p —SO 3   − M + ,    R 4  is —(CH 2 ) s —O—(CH 2 ) p —SO 3   − M + ,    m and n are an integer from 0 to 3,    M +  is a cation,    s is an integer from 0 to 10, and    p is an integer from 1 to 18, and    b) removing water from the mixture resulting in step a).    
     
     
         19 . A process for the antistatic finishing of photographic material comprising applying a dispersion or a solution to a photographic material, 
 wherein the dispersion or the solution contains a polythiophene + An −  ion complex in an organic solvent, and the solution or the dispersion prepared by a process comprising,    a) adding a water-miscible organic solvent or a water-miscible organic solvent mixture to an aqueous dispersion or a solution of polythiophene + An −  ion complex,    wherein the polythiophene +  is a polymer comprising recurring units selected from the group consisting of recurring units represented by the following formula (I) and formula (II),                          at least some of which are positively charged and in which for formula (I).    Y is —(CH 2 ) m —CR 1 R 2 (CH 2 ) n — or an optionally substituted 1,2-C 3 -C 8 -cycloalkylene radical, and    R 1  and R 2 , independently of one another, are hydrogen, hydroxymethyl, an optionally substituted C 1 -C 20 -alkyl radical or an optionally substituted C 6 -C 14 -aryl radical, and    m and n are identical or different and are an integer from 0 to 3, and further wherein,    An −  is an anion of an organic polyacid, and for formula (II)                          at least some of the thiophene rings carry a positive charge, and    Z is —(CH 2 ) m —CR 3 R 4 (CH 2 ) n —,    R 3  is hydrogen or —(CH 2 ) s —O—(CH 2 ) p —SO 3   − M + ,    R 4  is —(CH 2 ) s —O—(CH 2 ) p —SO 3   − M + ,    m and n are an integer from 0 to 3,    M +  is a cation,    s is an integer from 0 to 10, and    p is an integer from 1 to 18, and    b) removing water from the mixture resulting in step a).