Aniline copolymers and methods for their preparation and use

Abstract

Aniline copolymers and methods of making these copolymers are disclosed herein. The copolymers can, for example, be used for removing metal ions from a sample.

1 . A copolymer comprising at least one optionally substituted 2-hydroxy-5-sulfonic aniline as a first monomer unit and at least one aniline as a second monomer unit. 
     
     
         2 . The copolymer of  claim 2 , wherein the first monomer unit is represented by Formula I: 
       
         
           
           
               
               
           
         
         wherein R 1  is hydrogen or an electron-donating group, and R 2  is hydrogen or an electron-donating group. 
       
     
     
         3 . The copolymer of  claim 2 , wherein R 1  is hydrogen and R 2  is hydrogen. 
     
     
         4 . The copolymer of  claim 2 , wherein the electron-donating group is C 1-6  alkyl. 
     
     
         5 . The copolymer of  claim 1 , wherein the copolymer comprises at least about 5% of the first monomer unit by mole. 
     
     
         6 . The copolymer of  claim 5 , wherein the copolymer comprises at least about 10% of the first monomer unit by mole. 
     
     
         7 . The copolymer of  claim 6 , wherein the copolymer comprises about 20% of the first monomer unit by mole. 
     
     
         8 . The copolymer of  claim 1 , wherein the copolymer has a molar ratio of the first monomer unit to the second monomer unit from about 1:99 to about 50:50. 
     
     
         9 . The copolymer of  claim 8 , wherein the molar ratio of the first monomer unit to the second monomer unit is about 20:80. 
     
     
         10 . A composition comprising submicroparticles, wherein the submicroparticles comprise a copolymer of  claim 1 . 
     
     
         11 . The composition of  claim 10 , wherein the submicroparticles have an average size of about 50 nm to about 5 μm. 
     
     
         12 . The composition of  claim 10 , wherein the submicroparticles have an average bulk electrical conductivity of about 10 −7  S/cm to about 100 S/cm. 
     
     
         13 . The composition of  claim 10 , wherein the submicroparticles have an average surface size of about 1 m 2 /g to about 500 m 2 /g. 
     
     
         14 . The composition of  claim 10 , wherein the submicroparticles have an average pore diameter of about 1 nm to about 500 nm. 
     
     
         15 . A method of making a copolymer, the method comprising:
 forming a composition comprising at least one oxidizing agent, at least one optionally substituted 2-hydroxy-5-sulfonic aniline monomer, and at least one aniline monomer; and   maintaining the composition under conditions effective to polymerize the 2-hydroxy-5-sulfonic aniline monomer and the aniline monomer to form the copolymer.   
     
     
         16 . The method of  claim 15 , wherein the optionally substituted 2-hydroxy-5-sulfonic aniline monomer is represented by Formula I: 
       
         
           
           
               
               
           
         
         wherein R 1  is hydrogen or an electron-donating group, and R 2  is hydrogen or an electron-donating group. 
       
     
     
         17 . The method of  claim 15 , wherein the oxidizing agent is selected from the group consisting of ammonium persulfate, sodium persulfate, potassium persulfate, FeCl 3 , potassium iodate, Na 3 VO 4 , benzoyl peroxide (BPO), and any combination thereof. 
     
     
         18 . The method of  claim 17 , wherein the oxidizing agent is ammonium persulfate. 
     
     
         19 . The method of  claim 15 , wherein the molar ratio of the optionally substituted 2-hydroxy-5-sulfonic aniline monomer to the aniline monomer is about 1:99 to about 50:50. 
     
     
         20 . The method of  claim 18 , wherein the molar ratio of the optionally substituted 2-hydroxy-5-sulfonic aniline monomer to the aniline monomer is about 20:80. 
     
     
         21 . The method of  claim 15 , wherein the molar ratio of the oxidizing agent to a total amount of monomer components in the composition is about 0.5:1 to about 5:1. 
     
     
         22 . The method of  claim 21 , wherein the molar ratio of the oxidizing agent to a total amount of monomer components in the composition is about 1:1. 
     
     
         23 . The method of  claim 15 , wherein the composition is maintained at a temperature of about 0° C. to about 100° C. 
     
     
         24 . The method of  claim 23 , wherein the composition is maintained at a temperature of about 30° C. 
     
     
         25 . The method of  claim 15 , wherein forming the composition comprises combining a first solution comprising a first solvent and the oxidizing agent; and a second solution comprising a second solvent, the optionally substituted 2-hydroxy-5-sulfonic aniline monomer, and the aniline monomer, wherein the optionally substituted 2-hydroxy-5-sulfonic aniline monomer and the aniline monomer are soluble in the first and second solvents. 
     
     
         26 . The method of  claim 25 , wherein the second solvent is an acidic aqueous medium. 
     
     
         27 . The method of  claim 26 , wherein the acidic aqueous medium comprises an acid selected from the group consisting of HCl, HNO 3 , H 2 SO 4 , HClO 4 , H 3 PO 4 , H 5 IO 6 , CH 3 COOH, and any combination thereof. 
     
     
         28 . The method of  claim 15 , wherein the maintaining step is performed for about 2 hours to about 48 hours. 
     
     
         29 .- 50 . (canceled)