Synthesis of functionalizable or functionalized poly(3,4-ethylenedioxythiphene)-based polymers and monomers therefor

Abstract

A method of forming a compound having the formula:includes the reaction:n the presence of a base comprising teat-butyl lithium, lithium diisopropylamide, sodium hydroxide, potassium hydroxide, lithium hydroxide, a potassium alkoxide or a sodium alkoxide to achieve a yield of at least 90%, wherein X is a halo atom selected from the group consisting of Cl, Br and I.

What is claimed is: 
     
         1 . A method of forming the compound: 
       
         
           
           
               
               
           
         
         comprising, the reaction: 
       
       
         
           
           
               
               
           
         
         in the presence of a base comprising teat-butyl lithium, lithium diisopropylamide, sodium hydroxide, potassium hydroxide, lithium hydroxide, a potassium alkoxide or a sodium alkoxide to achieve a yield of at least 90%, wherein X is a halo atom selected from the group consisting of Cl, Br and I. 
       
     
     
         2 . The method of  claim 1  wherein a conjugate acid of the base has a pKa of at least 17. 
     
     
         3 . The method of  claim 1  wherein the reaction takes place under conditions to limit nucleophilic addition reactions by the base. 
     
     
         4 . The method of  claim 1  wherein the base is a non-nucleophilic base. 
     
     
         5 . The method of  claim 1  wherein the base comprises potassium tert-butoxide and sodium tert-butoxide. 
     
     
         6 . The method of  claim 1  wherein the base comprises potassium tert-butoxide. 
     
     
         7 . The method of  claim 6  wherein the reaction take place at room temperature. 
     
     
         8 . The method of  claim 1  wherein the reaction occurs at a temperature in the range of approximately 0° C. to 100° C. 
     
     
         9 . The method of  claim 1  wherein the reaction proceeds to quantitative conversion. 
     
     
         10 . The method of  claim 1  wherein the base comprises sodium hydroxide and potassium hydroxide. 
     
     
         11 . The method of  claim 1  wherein the reaction has a yield of at least 95%. 
     
     
         12 . The method of  claim 1  wherein X is Cl. 
     
     
         13 . A method of forming a polymer, comprising; polymerizing monomers comprising at least one of exomethylene functionalized 3,4-ethylenedioxythiophene or the reaction product of exomethylene functionalized 3,4-ethylenedioxythiophene and a compound including a group reactive with the exomethylene group of exomethylene functionalized 3,4-ethylenedioxythiophene via a polymerization reaction, wherein the monomers have a purity of at least 90% in the polymerization reaction. 
     
     
         14 . The method of  claim 13  wherein the monomers have a purity of at least 95%. 
     
     
         15 . The method of  claim 13  wherein the polymerization reaction is an electropolymerization reaction and the method further comprises functionalization of the polymer after synthesis by reacting a compound with an exomethylene group. 
     
     
         16 . The method of  claim 13  wherein the monomers have a concentration of at least 20 mM in the polymerization reaction. 
     
     
         17 . The method of  claim 13  wherein the group reactive with the exomethylene group is a thiol group. 
     
     
         18 . The method of  claim 13  wherein the compound including the group reactive with the exomethylene group is selected from the group consisting of 3-mercaptopropionic acid, 3-Chloro-1-propanethiol, 1-mercapto-2-propanol, 3-mereapto-1-propanol, 3-amino-1-propanethiol hydrochloride, 4-mercapto-1-butano, 6-mercaptohexanoic acid, 6-mercapto-1-hexanol, 6-mercapto-1-hexanol, 6-amino-1-hexanethiol hydrochloride, 8-mercaptooctanoic acid, 8-mercapto-1-octanol, 8-amino-1-octanethiol hydrochloride, 9-mercapto-1-nonanol, 11-mercaptoundecanoic acid, 11-mercaptoundec anamide, 11-azido-1-undecanethiol, 11-mercapto-1-undecanol, 11-amino-1-undecanethiol hydrochloride, 11-mercaptoundecylphosphonic acid, 11-mercaptoundecylphosphoric acid, 12-mercaptododecanoic acid, 1-(11-mercaptoundecyl)imidazole, (11-mercaptound ecyl)-N,N,N-trimethylammonium bromide, 11-(1H-pyrrol-1-yl)undecane-1-thiol, 6-(ferrocenyl)hexanethiol, 12-mercaptododecanoic acid NHS ester, 16-mercaptohexadecanoic acid, 16-mercaptohexadecanamide, 16-amino-1-hexadecanethiol hydrochloride, 11-mercaptoundecylhydroquinone, triethylene glycol mono-11-mercaptoundecyl ether, (11-mercaptoundecyl)tetra(ethylene glycol), 11-(ferrocenyl)undecanethiol, (11-mercaptoundecyl)hexa(ethylene glycol), or a biomolecule. 
     
     
         19 . The method of  claim 18  wherein the biomolecule is a zwitterionic amino acid cysteine, a peptide, a protein, or a nucleic acid. 
     
     
         20 . A method of forming a polymer, comprising: polymerizing monomers comprising at least one of exomethylene functionalized 3,4-ethylenedioxythiophene or the reaction product of exomethylene functionalized 3,4-ethylenedioxythiophene and a compound including a group reactive with the exomethylene group of exomethylene functionalized 3,4-ethylenedioxythiophene via a polymerization reaction, wherein the monomers have a concentration of at least 20 mM in the polymerization reaction.