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 - 19 . (canceled) 
     
     
         20 . 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 polyimide; and 
         (b) at least one organic solvent, wherein the dispersion or solution has a water content from 0 to 20% by weight and said organic solvent is 
         a) amidic solvent; 
         b) a solvent having a boiling point of above 100° C. at atmospheric pressure, or a water-miscible solvent forming an azeotrope with water; 
         c) ethylene glycol dimethyl ether, ethylene glycol monomethyl ether or ethylene glycol monobutyl ether; 
         d) solvent mixed with sugar alcohols; 
         e) dioxane; 
         f) tetrahydrofuran; or 
         g) esters of aliphatic and aromatic carboxylic acid, 
         the content of the ion complexes in the dispersion or solution being from 0.2 to about 20% by weight. 
       
     
     
         21 . The dispersion or the solution as claimed in  claim 20 , wherein the organic solvent is ethylene glycol or glycerol. 
     
     
         22 . The dispersion or the solution as claimed in  claim 20 , wherein the content of the ion complexes in the dispersion or solution being from 0.2 to 5% by weight. 
     
     
         23 . The dispersion or the solution as claimed in  claim 20 , wherein the dispersion or solution is obtained by
 a) adding said organic solvent to an aqueous dispersion or solution comprising said polythiophene + An −  ion complex optionally substituted polythiophenes, and   b) removing at least some of the water from the resultant mixtures by distillation.   
     
     
         24 . A process for the preparation of dispersions or solutions comprising optionally substituted polythiophenes in organic solvents, which comprises
 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 resultant mixtures by distillation.   
     
     
         25 . A process for the preparation of dispersions or solutions comprising polythiophene + An −  ion complexes in organic solvents, which comprises
 a) adding a water-miscible organic solvent or a water-miscible organic solvent mixture to an aqueous dispersion or solution of polythiophene + An −  ion complexes, where polythiophene +  is a polymer which comprises recurring units of the formula (I) 
 
       
         
           
           
               
               
           
         
         at least some of which are positively charged and 
         in which 
         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 where 
         An −  is an anion of an organic polyacid, 
         or where 
         polythiophene + An −  is a polymer which comprises recurring units of the formula (II) 
       
       
         
           
           
               
               
           
         
         in which at least some of the thiophene rings carry a positive charge and 
         in which 
         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 resultant mixtures by distillation. 
       
     
     
         26 . The process according to  claim 24 , wherein the process further comprises diluting the resultant dispersion or solution with an organic solvent or a mixture of organic solvents subsequent to step b). 
     
     
         27 . The process according to  claim 25 , wherein the process further comprises diluting the resultant dispersion or solution with an organic solvent or a mixture of organic solvents subsequent to step b). 
     
     
         28 . The process according to  claim 25 , wherein the aqueous dispersions or solutions employed for step a) comprise polythiophene+An− ion complexes where polythiophene+ is a polymer which comprises recurring units of the formula (I), at least some of which are positively charged and in which
 Y is —(CH 2 ) m —CR 1 R 2 (CH 2 ) n — or a 1,2-cyclohexylene radical, and 
 R 1  and R 2 , independently of one another, are hydrogen, hydroxymethyl, C 1 -C 8 -alkyl or phenyl, and 
 m and n are identical or different and are 0 or 1, 
 and where 
 An −  is an anion of a polyacrylic acid, polyvinylsulphonic acid, polystyrenesulphonic acid, a mixture thereof or a copolymer of the parent monomers or copolymers with acid-free monomers. 
 
     
     
         29 . The process according to  claim 25 , wherein the aqueous dispersions or solutions employed for step a) comprise polythiophene + An −  complexes where polythiophene + An −  is a polymer which comprises recurring units of the formula (II) in which at least some of the thiophene rings carry a positive charge and in which
 Z is —(CH 2 ) m —CR 1 R 2 (CH 2 ) n —, 
 R 3  is hydrogen, 
 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 0, 1 or 2, 
 p is 4 or 5. 
 
     
     
         30 . The process according to  claim 25 , wherein the aqueous dispersions or solutions employed in step a) comprise polythiophene + An −  ion complexes where polythiophene + An −  is a polymer which comprises recurring units of the formula (I), at least some of which are positively charged and
 in which 
 Y is a 1,2-ethylene radical, 
 and where 
 An −  is an anion of a polystyrenesulphonic acid. 
 
     
     
         31 . The process according to  claim 25 , wherein the aqueous dispersions or solutions employed for step a) comprise polythiophene + An −  complexes where polythiophene + An −  is a polymer which comprises recurring units of the formula (II) in which at least some of the thiophene rings carry a positive charge and in which
 Z is —(CH 2 ) m —CR 3 R 4 (CH 2 ) n —, 
 R 3  is hydrogen, 
 R 4  is —(CH 2 ) s —O—(CH 2 ) p —SO 3   − M + , 
 m is 1, 
 n is 0 or 1, 
 M +  is a cation, 
 s is 0 or 1, 
 p is 4. 
 
     
     
         32 . The process according to  claim 24 , wherein the starting material used is an aqueous dispersion or solution of a polythiophene + An −  ion complex which has been fully or partially freed from the inorganic salt content.