Anti-oxidant macromonomers and polymers and methods of making and using the same

Abstract

Methods of preparing an antioxidant polymer are described comprising polymerizing macromonomers that comprise an antioxidant. By having the antioxidant as part of the macromonomer, a polymer with a higher density of antioxidants is prepared more efficiently than coordinating antioxidants to an already formed polymer. The methods of polymerization also encompass copolymerization wherein different macromonomers comprising different antioxidants may be used. Alternatively, the other macromonomer, or monomer, may not include an antioxidant depending on the intended use of the copolymer and desired properties. The macromonomer comprising a antioxidant may comprise more than one antioxidant which may be the same or different. In one embodiment, the macromonomer is benzene or olefin based, wherein the benzene or olefin is substituted with an antioxidant.

1 . A method of preparing an antioxidant polymer comprising polymerizing a macromonomer comprising an antioxidant moiety.  
   
   
       2 . The method of  claim 1 , wherein polymerization is carried out with a catalyst selected from the group consisting of a peroxidase, laccase, tyosinase, lipase, hematin, metal-salen complex, metallocene, a cationic initiator, an anionic initiator, a radical initiator, or a metal halide.  
   
   
       3 . The method of  claim 2 , wherein the catalyst is selected from the group comprising: 
 a) horse radish peroxidase (HRP);    b) a Fe-salen complex; and    c) AIBN.    
   
   
       4 - 5 . (canceled)  
   
   
       6 . The method of  claim 1 , wherein the macromonomer comprises a benzene ring, or the macromonomer is an alkene, wherein the benzene ring or the alkene is substituted with an antioxidant moiety.  
   
   
       7 . The method of  claim 6  macromonomer wherein the antioxidant moiety comprises a hydroxy substituted benzene ring.  
   
   
       8 - 9 . (canceled)  
   
   
       10 . The method of  claim 1 , wherein the antioxidant moiety comprises a hydroxy substituted benzene ring.  
   
   
       11 . The method of  claim 10 , wherein the benzene ring is further substituted with at least one bulky alkyl group.  
   
   
       12 . The method of  claim 11 , wherein the bulky alkyl group is a t-butyl group.  
   
   
       13 . The method of  claim 12 , wherein the t-butyl group is adjacent to the hydroxy group.  
   
   
       14 . The method of  claim 13 , wherein the benzene ring is substituted with two t-butyl groups adjacent to the hydroxy group.  
   
   
       15 . The method of  claim 1 , wherein the macromonomer is represented by the following structural formula:  
     
       
         
         
             
             
         
       
     
     wherein, independently for each occurrence: 
 n and m are integers from 0 to 18, inclusive;  
 Z is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH═N—, —N═CH—, —C(O)—, —O—.—S—.—S—S—, —S═N—, —N═S—, —C(S)O—, —OC(S)—, —OP(O)(OR 4 )O—, —OP(OR 4 )O—, —C(O)OC(O)— or a bond;  
 R is —H, C 1-6  alkyl, —OH, —NH 2 , —SH, aryl, ester or  
                     
 wherein at least one R adjacent to the —OH group is a bulky alkyl group;  
 R 1  is —H, C 1-6  alkyl, aryl, aralkyl, —OH, —NH 2 , —SH or ester,  
 wherein at least one R 1  adjacent to the —OH group is a bulky alkyl group;  
 R 4  is —H, C 1-6  alkyl, aryl, aralkyl, heteroaryl or heteroararalkyl; and  
 M is:  
                     
 R 2  is —H, C 1-6  alkyl, —OH, —NH 2 , —SH aryl, ester or  
                     
 wherein at least one R 2  is —OH; and  
 R 3  is —H, C 1-6  alkyl, aryl, aralkyl, —OH, —NH 2 , —SH or ester.  
 
   
   
       16 . The method of  claim 15 , wherein polymerization is carried out with a catalyst selected from the group consisting of a peroxidase, laccase, tyosinase, lipase, hematin, metal-salen complex, metallocene, a cationic initiator, an anionic initiator, a radical initiator, or a metal halide.  
   
   
       17 . The method of  claim 16 , wherein the catalyst is selected from the group comprising: 
 a) horse radish peroxidase (HRP);    b) a Fe-salen complex; and    c) AIBN.    
   
   
       18 - 38 . (canceled)  
   
   
       39 . The method of  claim 15 , wherein both R groups adjacent to —OH are bulkyl alkyl groups.  
   
   
       40 . The method of  claim 15 , wherein both R groups adjacent to —OH are t-butyl.  
   
   
       41 - 47 . (canceled)  
   
   
       48 . The method of  claim 15 , wherein n is 0, m is 1, Z is —C(O)O—, and the two R groups adjacent to the —OH are t-butyl.  
   
   
       49 . The method of  claim 48 , wherein M is:  
     
       
         
         
             
             
         
       
     
   
   
       50 . The method of  claim 49 , wherein the R 2  in the para position is —OH.  
   
   
       51 . The method of  claim 50 , wherein at least one R 2  adjacent to the para position is OH.  
   
   
       52 . The method of  claim 51 , wherein and the two R 2  groups adjacent to the para position are OH.  
   
   
       53 - 54 . (canceled)  
   
   
       55 . The method of  claim 1  comprising polymerizing a macromonomer represented by the following structural formaul at least one other different monomer.  
     
       
         
         
             
             
         
       
     
     wherein, independently for each occurrence: 
 n and m are integers from 0 to 18, inclusive;  
 Z is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —CH═N—, —N═CH—, —C(O)—, —O—.—S—.—S—S—, —S═N—, —N═S—, —C(S)O—, —OC(S)—, —OP(O)(OR 4 )O—, —OP(OR 4 )O—, —C(O)OC(O)— or a bond;  
 R is —H, C 1-6  alkyl, —OH, —NH 2 , —SH, aryl, ester or  
                     
 wherein at least one R adjacent to the —OH group is a bulky alkyl group;  
 R 1  is —H, C 1-6  alkyl, aryl, aralkyl, —OH, —NH 2 , —SH or ester, wherein at least one R 1  adjacent to the —OH group is a bulky alkyl group;  
 R 4  is —H, C 1-6  alkyl, aryl, aralkyl, heteroaryl or heteroararalkyl; and  
 M is:  
                     
 R 2  is —H, C 1-6  alkyl, —OH, —NH 2 , —SH aryl, ester or  
                     
 wherein at least one R 2  is —OH; and  
 R 3  is —H, C 1-6  alkyl, aryl, aralkyl, —OH, —NH 2 , —SH or ester.  
 
   
   
       56 - 59 . (canceled)  
   
   
       60 . The method of  claim 55 , wherein the different monomer comprises an antioxidant moiety.  
   
   
       61 . The method of  claim 55 , wherein the antioxidant polymer is a random copolymer or a block copolymer.  
   
   
       62 - 63 . (canceled)