Conductive polymers having highly enhanced solubility in organic solvent and electrical conductivity and synthesizing process thereof

Abstract

The present invention relates to a new process of synthesizing conductive polymers from monomers substituted with amine group. The process provides simple synthesizing steps for the conductive polymers without using other additives such as stabilizers or emulsifiers. The conductive polymers synthesized according to the present invention have highly enhanced solubility in common organic solvents and electrical conductivity compared to conventional conductive polymers. Therefore, the conductive polymers synthesized according to the present process can be utilized in applications that require high electrical conductivity, for example an electromagnetic interference shield or a transparent electrode of thin film, as well as in specific applications such as various conductive films, fibers, polymer blends, battery electrodes or conductive etch mask layers.

1 . A process of synthesizing a conductive polymer, the process comprising: 
 (a) mixing a monomer substituted with an amine group and an organic solvent with an acid solution; and    (b) adding a radical initiator dissolved in a protonic acid into the acid solution to synthesize the conductive polymer.    
   
   
       2 . The process according to  claim 1 , wherein the monomer substituted with the amine group is mixed with the acid solution prior to the organic solvent.  
   
   
       3 . The process according to  claim 1 , wherein the monomer substituted with the amine group has a structure represented by formula I below.  
     
       
         
         
             
             
         
       
       wherein R 1  is hydrogen, alkyl, or alkoxy group; and each R 2  to R 5  is respectively hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkyl-thioalkyl, alkanoyl, thioalkyl, aryl-alkyl, alkyl-amino, amino, alkoxy carbonyl, alkyl sulfonyl, alkyl sulfinyl, thioaryl, sulfonyl, carboxyl, hydroxyl, halogen, nitro, or alkyl-aryl.  
     
   
   
       4 . The process according to  claim 1 , wherein the monomer substituted with the amino group has a structure represented by formula II below.  
     
       
         
         
             
             
         
       
       wherein R 1  is hydrogen, alkyl, or alkoxy group; and each R 2  and R 3  is respectively hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkyl-thioalkyl, alkanoyl, thioalkyl, aryl-alkyl, alkyl-amino, amino, alkoxy carbonyl, alkyl sulfonyl, alkyl sulfinyl, thioaryl, sulfonyl, carboxyl, hydroxyl, halogen, nitro, or alkyl-aryl.  
     
   
   
       5 . The process according to  claim 1 , wherein the acid comprises inorganic acid.  
   
   
       6 . The process according to  claim 1 , wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid.  
   
   
       7 . The process according to  claim 1 , wherein the protonic acid comprises an inorganic acid.  
   
   
       8 . The process according to  claim 7 , wherein the inorganic acid is selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, or hydroiodic acid or mixtures thereof.  
   
   
       9 . The process according to  claim 1 , wherein the protonic acid comprises an organic acid.  
   
   
       10 . The process according to  claim 9 , wherein the organic acid is selected from the group consisting of methyl sulfonic acid, dodecyl benzene sulfonic acid, antraquinone-2-sulfonic acid, 4-sulfosalicylic acid, camphor sulfonic acid, chlorinated sulfonic acid, trifluoro-sulfonic acid.  
   
   
       11 . The process according to  claim 1 , wherein the organic solvent has a solubility parameter of about 17 to about 29.  
   
   
       12 . The process according to  claim 1 , wherein the organic solvent comprises hydrocarbons unsubstituted or substituted with hydroxyl, halogen, oxygen, ketone, or carboxyl group.  
   
   
       13 . The process according to  claim 1 , wherein the organic solvent is an alkyl halide.  
   
   
       14 . The process according to  claim 1 , wherein the organic solvent comprises dichloromethane, pentachloro ethane, 1,1,2,2-tetrachloro ethane, trichloro ethane, trichloro ethylene, dichloro methane, chloroform, ethyl bromide, ethyl chloride, dichloro propane, trichloro ethane, bis(2-chloroethyl)ether, dichloro ethyl ether, 1,2-dichloro benzene, or mixtures thereof.  
   
   
       15 . The process according to  claim 1 , wherein the organic solvent is selected from the group consisting of comprise 1-propanol, 2-methyl-2-propanol, 1,2-dipropandiol, 1,3-propandiol, isopropyl alcohol, butanol, neopentanol, 2-methoxy ethanol, 2-butoxy ethanol, 2-ethyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1,2-propanediol, 1,5-pentandiol, amylalcohol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl3-pentanol, hexanol, ethyl hexanol, heptanol, 3-heptanol, 2-methyl-2,4-pentandiol, 2-ethyl-1,3-hexandiol, octanol, 1-octanol, 2-octanol, decanol, dodecanol, cyclohexanol, tri-ethylene glycol, di-ethylene glycol, tetra-ethylene glycol, tetra-hydrofurfuryl alcohol, or mixtures thereof.  
   
   
       16 . The process according to  claim 1 , wherein the organic solvent comprises ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether or diethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, 1,4-dioxane, or mixtures thereof.  
   
   
       17 . The process according to  claim 1 , wherein the organic solvent comprises butyl methyl ketone, methyl-ethyl ketone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, diacetone alcohol, 4-methyhl-pentanone, 4-methyl-2-pentanone, or mixtures thereof.  
   
   
       18 . The process according to  claim 1 , wherein the organic solvent comprises diethyl carbonate, benzyl acetate, dimethyl glutarate, ethylacetoacetate, isobutyl isobutanoate, isobutyl acetate, meta-cresol, toluene, xylene, nitrobenzene, tetrahydrofuran, N-methyl-2-pyrolidone, dimethyl sulfoxide, N,N-dimethylformamide, or mixtures thereof.  
   
   
       19 . The process according to  claim 1 , wherein the radical initiator comprises ammonium persulfate, hydrogen peroxide, manganese dioxide, potassium dichromate, potassium iodate, ferric chloride, potassium permanganate, potassium bromate, potassium chlorate, or mixtures thereof.  
   
   
       20 . The process according to  claim 1 , wherein step (b) is performed in the temperature of between about −45° C. to about 40° C.  
   
   
       21 . The process according to  claim 1 , wherein the radical initiator and the organic solvent comprises an organic phase, wherein the organic phase comprises about 5˜95% by weight based upon total aqueous solution.  
   
   
       22 . The process according to  claim 2 , further comprising step (c) dedoping the conductive polymer with a base.  
   
   
       23 . The process according to  claim 22 , wherein the base comprises hydroxide compounds.  
   
   
       24 . A conductive polymer synthesized according to  claim 1 , wherein the conductive polymer has a hollow quadra-angular rod shape and honeycombed network configuration.  
   
   
       25 . The conductive polymer according to  claim 24 , wherein the conductive polymer is consisted of nanometer particles.  
   
   
       26 . The conductive polymer according to  claim 24 , wherein the conductive polymer is consisted of nanometer tubes.  
   
   
       27 . The conductive polymer according to  claim 24 , wherein the conductive polymer is consisted of nano-fibers.  
   
   
       28 . The conductive polymer according to  claim 24 , wherein the conductive polymer has an apparent density in the range of about 0.03˜0.19 measured in ASTM Standard D1895-6.  
   
   
       29 . A conductive polymer synthesized according to  claim 1 , wherein the conductive polymer has an electrical conductivity of at least about 300 S/cm.  
   
   
       30 . The conductive polymer according to  claim 29 , wherein the conductive polymer has an electrical conductivity of at least about 500 S/cm.  
   
   
       31 . The conductive polymer according to  claim 29 , wherein the conductive polymer has an electrical conductivity of at least about 700 S/cm.  
   
   
       32 . The conductive polymer according to  claim 29 , wherein the conductive polymer has an electrical conductivity of at least about 900 S/cm.  
   
   
       33 . The conductive polymer according to  claim 29 , wherein the conductive polymer has an electrical conductivity is at least about 1100 S/cm.  
   
   
       34 . The conductive polymer according to  claim 27 , wherein the conductive polymer has an electrical conductivity of at least about 1300 S/cm.  
   
   
       35 . A conductive polymer synthesized according to  claim 22 , wherein the conductive polymer has a hollow quadra-angular rod shape and honeycombed network configuration, wherein the conductive polymer has a repeat unit represented by the formula below and the conductive polymer has at least one single peak at about 123 ppm of chemical shift and at about 158 ppm of chemical shift in a  13 C CPMAS NMR spectrum and/or has identifiable peaks at around 140 ppm of chemical shift in a  13 C CPMAS NMR spectrum.  
     
       
         
         
             
             
         
       
       wherein x and y is respectively a molar fraction of quinonediimine structural unit and phenylenediamine structural unit in the repeating unit, and 0<x<1, 0<y<1 and x+y=1; and n is an integer of 2 or more.  
     
   
   
       36 . The conductive polymer according to  claim 35 , wherein the conductive polymer forms peaks at about 138 ppm of chemical shift and at about 143 ppm of chemical shift in a  13 C CPMAS NMR spectrum.  
   
   
       37 . The conductive polymer according to  claim 35 , wherein the conductive polymer has I 138  larger than I 143 , wherein I 138  represents a peak intensity at about 138 ppm of chemical shift in the  13 C CPMAS NMR spectrum and I 143  represents a peak intensity at about 143 ppm of chemical shift in the  13 C CPMAS NMR spectrum.  
   
   
       38 . The conductive polymer according to  claim 37 , wherein the conductive polymer has a peak intensity ratio, I  138 /I 143 , of equal to or more than 1.2 in the  13 C CPMAS NMR spectrum.  
   
   
       39 . The conductive polymer according to  claim 35 , wherein the conductive polymer has two peaks at about wavelength 1107 cm −1  in PAS spectrum.  
   
   
       40 . A polyaniline having a repeat unit represented by the formula below, wherein the polyaniline has three main peaks corresponding to quaternary carbon in a solution state  13 C NMR spectrum in case the polyaniline is substituted with tert-butoxycarbonyl. 
 [Formula]                         wherein x and y is respectively a molar fraction of a quinonediimine structural unit and phenylenediamine structural unit in the repeating unit, and 0<x<1, 0<y<1 and x+y=1; and n is an integer of 2 or more.