Polymerizable sulfonate ionic liquids and liquid polymers therefrom

Abstract

Disclosed is a new ionic liquid monomer salt and methods of is synthesis and polymerization. The ionic liquid monomer salt is prepared by mixing equimolar amounts of an amine, such as tris[2-(2-methoxyethoxy)-ethyl]amine and an acid functionalized polymerizable monomer, such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), which is stirred at ambient temperature until salt formation is complete. Also disclosed is a new ionic liquid polymer salts and method for making the same. The synthesis of AMPS 2-acrylamido-2-methyl-1-propanesulfonic acid-ammonium salt polymer is accomplished by adding 2,2′-azobisisobutyronitrile (AIBN) to the ionic liquid monomer salt and heating the homogeneous melt at 70° C. for 18 hr.

1. An ionic liquid monomer salt having the general formula: 
       
         
           
           
               
               
           
         
       
       wherein A=H or CH 3 ;
 X═—COY—, -p-C 6 H 4 —, -o-C 6 H 4 —, -m-C 6 H 4 —, —O—, or —CH 2 —; 
 Y═—O(CH 2 ) n — where n=1 to 4, or
 —(OCH 2 CH 2 ) n — where n=1 to 6, or 
 —NHCH(CH 3 )—, —NHC(CH 3 ) 2 —, —N(C 12 H 25 )CH 2 CH 2 —, 
 —NHC(CH 3 ) 2 CH 2 —, or —NHCH(C 6 H 5 )CH 2 —, 
 
 
       wherein R is selected from
 —(CH 2 CH 2 O) n CH 3  where n=1 to 4, or   —(CH 2 ) 3 (Si(CH 3 ) 2 O) n CH 3  where n=1 to 6, or   —(CF 2 ) n CF 3  or —CH 2 (CF 2 ) n CF 3  where n=1 to 8;   
       wherein R, R′, and/or R″ are each independently selected from —H or
 —(CH 2 ) n CH 3  where n=1 to 12, or 
 —(CH 2 CH 2 O) n CH 3  where n=1 to 4, or 
 —(CH 2 ) 3 (Si(CH 3 ) 2 O) n CH 3  where n=1 to 6, or 
 —(CF 2 ) n CF 3 , or —CH 2 (CF 2 ) n CF 3  where n=1 to 8. 
 
     
     
       2. An ionic liquid polymer salt having the general formula: 
       
         
           
           
               
               
           
         
       
       wherein m>1;
 A=H or CH 3 ; 
 X═—COY—, -p-C 6 H 4 —, -o-C 6 H 4 —, -m-C 6 H 4 —, —O—, or —CH 2 —; 
 Y═—O(CH 2 ) n — where n=1 to 4, or
 —(OCH 2 CH 2 ) n — where n=1 to 6, or 
 —NHCH(CH 3 )—, —NHC(CH 3 ) 2 —, —N(C 12 H 25 )CH 2 CH 2 —, 
 —NHC(CH 3 ) 2 CH 2 —, or —NHCH(C 6 H 5 )CH 2 —; 
 
 
       wherein R is selected from
 —(CH 2 CH 2 O) n CH 3  where n=1 to 4, or   —(CH 2 ) 3 (Si(CH 3 ) 2 O) n CH 3  where n=1 to 6, or   —(CF 2 ) n CF 3  or —CH 2 (CF 2 ) n CF 3  where n=1 to 8;   
       wherein R, R′, and/or R″ are each independently selected from —H or
 —(CH 2 ) n CH 3  where n=1 to 12, or 
 —(CH 2 CH 2 O) n CH 3  where n=1 to 4, or 
 —(CH 2 ) 3 (Si(CH 3 ) 2 O) n CH 3  where n=1 to 6, or 
 —(CF 2 ) n CF 3 , or —CH 2 (CF 2 ) n CF 3  where n=1 to 8. 
 
     
     
       3. A method for making an ionic liquid monomer salt comprising:
 mixing an equimolar amount of a sulfonic acid functionalized monomer having the general formula: 
 
       
         
           
           
               
               
           
         
       
       wherein A=H or CH 3 ;
 X═—COY—, -p-C 6 H 4 —, -o-C 6 H 4 —, -m-C 6 H 4 —, —O—, or —CH 2 —; 
 Y═—O(CH 2 ) n — where n=1 to 4, or
 —(OCH 2 CH 2 ) n — where n=1 to 6, or 
 —NHCH(CH 3 )—, —NHC(CH 3 ) 2 —, —N(C 12 H 25 )CH 2 CH 2 —, 
 —NHC(CH 3 ) 2 CH 2 —, or —NHCH(C 6 H 5 )CH 2 —; 
 
 
       with an organic amine base having the general formula: 
       
         
           
           
               
               
           
         
       
       wherein R is selected from
 —(CH 2 CH 2 O) n CH 3  where n=1 to 4, or   —(CH 2 ) 3 (Si(CH 3 ) 2 O) n CH 3  where n=1 to 6, or   —(CF 2 ) n CF 3  or —CH 2 (CF 2 ) n CF 3  where n=1 to 8;   
       wherein R, R′, and/or R″ are each independently selected from —H or
 —(CH 2 ) n CH 3  where n=1 to 12, or 
 —(CH 2 CH 2 O) n CH 3  where n=1 to 4, or 
 —(CH 2 ) 3 (Si(CH 3 ) 2 O) n CH 3  where n=1 to 6, or 
 —(CF 2 ) n CF 3 , or —CH 2 (CF 2 ) n CF 3  where n=1 to 8; and 
 
       stirring said mixture under an inert atmosphere until said sulfonic acid functionalized monomer is dissolved, wherein the dissolution completes formation of the ionic liquid monomer salt. 
     
     
       4. A method for making an ionic liquid polymer salt comprising:
 providing the ionic liquid monomer salt of  claim 1  having the general formula: 
 
       
         
           
           
               
               
           
         
       
       wherein A=H or CH 3 ;
 X═—COY—, -p-C 6 H 4 —, -o-C 6 H 4 —, -m-C 6 H 4 —, —O—, or —CH 2 —; 
 Y═—O(CH 2 ) n — where n=1 to 4, or
 —(OCH 2 CH 2 ) n  where n=1 to 6, or 
 —NHCH(CH 3 )—, —NHC(CH 3 ) 2 —, —N(C 12 H 25 )CH 2 CH 2 —, 
 —NHC(CH 3 )CH 2 —, or —NHCH(C 6 H 5 )CH 2 —; 
 
 
       wherein R, R′, and/or R″ are each independently selected from H or
 —(CH 2 ) n CH 3  where n=1 to 12, or 
 —(CH 2 CH 2 O) n CH 3  where n=1 to 4, or 
 —(CH) 3 (Si(CH 3 ) 2 O) n CH 3  where n=1 to 6, or 
 —(CF 2 ) n CF 3 , —CH 2 (CF 2 ) n CF 3  where n=1 to 8; 
 
       adding a free radical polymerization catalyst to said ionic liquid monomer salt; and 
       stirring said mixture under an inert atmosphere with application catalyst-specific polymerization conditions. 
     
     
       5. The ionic liquid monomer salt of claim 1, wherein the ionic liquid monomer salt has the formula: 
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       6. The ionic liquid polymer salt of claim 2, wherein the ionic liquid polymer salt has the formula: 
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       7. The method of claim 3;
 wherein the sulfonic acid functionalized monomer has the formula:   
       
         
           
           
               
               
           
         
         wherein the organic amine base has the formula: 
       
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       8. The method of claim 7, wherein the mixture further comprises methanol. 
     
     
       9. The method of claim 4, wherein the ionic liquid monomer salt has the formula: 
       
         
           
           
               
               
           
         
       
       
        
       
     
     
       10. The method of claim 9, wherein the mixture further comprises methanol. 
     
     
       11. The method of claim 9, wherein the free radical polymerization catalyst is 2,2′-azobisisobutyronitrile. 
     
     
       12. The method of claim 9, wherein the ratio of the monomer to the free radical polymerization catalyst is 100:1. 
     
     
       13. The method of claim 9, wherein the inert atmosphere is a nitrogen atmosphere. 
     
     
       14. The method of claim 9, wherein the catalyst-specific polymerization conditions are heating the mixture to about 70° C. 
     
     
       15. The method of claim 14, wherein the stirring and heating is conducted for about 18 hours.