Control agents for living-type free radical polymerization and methods of polymerizing

Abstract

Control agents that have an oxygen-nitrogen bond covalently bonded to a thiocarbonyl moiety are provided for living-type free radical polymerization of a wide variety of monomers, particularly vinyl monomers.

What is claimed is:  
     
         1 . A compound characterized by the general formula:  
       
         
           
           
               
               
           
         
         wherein R 1  is any group that can be expelled as its free radical form in an addition-fragmentation reaction;  
         R 2  and R 3  are each independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and combinations thereof, and optionally R 2  and R 3  are joined together in a ring structure having from 3 to 50 atoms in the backbone of the ring; also optionally, R 2  and R 3  are joined together to form a double bond optionally substituted alkenyl moiety.  
       
     
     
         2 . The compound of  claim 1 , wherein R 1  is selected from the group consisting of optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted amino and optionally substituted polymer chains.  
     
     
         3 . The compound of  claim 2 , wherein R 1  is selected from the group consisting of —CH 2 Ph, —CH(CH 3 )CO 2 CH 2 CH 3 , —CH(CO 2 CH 2 CH 3 ) 2 , —C(CH 3 ) 2 CN, CH(Ph)CN, —C(CH 3 ) 2 Ph, —CH(CH 3 )CN, and —CH 2 CH 2 CH 2 CH 3 .  
     
     
         4 . The compound of  claim 1 , wherein R 2  and R 3  are each independently selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally substituted, aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl optionally-substituted alkylphosphonyl, optionally substituted arylsulfinyl, and optionally substituted arylphosphonyl.  
     
     
         5 . The compound of  claim 1 , wherein R 2  and R 3  form an optionally substituted heterocycle ring.  
     
     
         6 . The compound of  claim 1 , wherein the compound is selected from the group consisting of:  
       
         
           
           
               
               
           
         
       
     
     
         7 . A compound characterized from any of the following general formulas:  
       
         
           
           
               
               
           
         
         wherein R 1  is any group that group that can be expelled as its free radical form in an addition-fragmentation reaction;  
         R 2  and R 3  are each independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, and combinations thereof; and optionally R 2  and R 3  together to form a double bond optionally substituted alkenyl moiety; and also optionally R 2  and R 3  together joined in a ring structure having from 3 to 50 atoms in the ring backbone;  
         Core is a core molecule;  
         c is 1 or more; and  
         d is 2 or more.  
       
     
     
         8 . The compound of  claim 7 , wherein R 1  is selected from the group consisting of optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted amino and optionally substituted polymer chains.  
     
     
         9 . The compound of  claim 8 , wherein R 1  is selected from the group consisting of —CH 2 Ph, —CH(CH 3 )CO 2 CH 2 CH 3 , —CH(CO 2 CH 2 CH 3 ) 2 , —C(CH 3 ) 2 CN, —CH(Ph)CN and —C(CH 3 ) 2 Ph, —CH(CH 3 )CN, —CH 2 CH 2 CH 2 CH 3 .  
     
     
         10 . The compound of  claim 7 , wherein R 2  and R 3  are each independently selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally substituted, aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkylphosphonyl, optionally substituted arylsulfinyl, and optionally substituted arylphosphonyl.  
     
     
         11 . The compound of  claim 7 , wherein wherein R 2  and R 3  form an optionally substituted heterocycle ring.  
     
     
         12 . The compound of  claim 7 , wherein Core is selected from the group consisting of:  
       
         
           
           
               
               
           
         
       
     
     
         13 . The compound of  claim 7 , wherein the compound is selected from the group consisting of: