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

Abstract

The present invention relates to macromonomer compounds possessing antioxidant properties, antioxidant polymers comprising the antioxidant macromonomers as a recurring unit, and methods of inhibiting oxidation in a substance comprising contacting the substance with the antioxidant polymers. In one embodiment, substantially all of the recurring macromonomeric units of the antioxidant polymers comprise an antioxidant moiety. In another embodiment, all of the recurring macromonomer units of the antioxidant polymers comprise an antioxidant moiety. The method of the present invention, yields antioxidant polymers with substantially all of the recurring units comprising an antioxidant moiety. These antioxidant polymers have greater bulk antioxidative properties than previously known.

1 . A polymer wherein substantially all the recurring monomeric units comprise an antioxidant moiety.  
   
   
       2 . (canceled)  
   
   
       3 . The polymer of  claim 1 , wherein the recurring monomeric unit is selected from the group comprising: 
 a) a benzene ring substituted with an antioxidant moiety; and    b) an alkenylene substituted with an antioxidant moiety.    
   
   
       4 . (canceled)  
   
   
       5 . The polymer of  claim 1 , wherein the antioxidant moiety comprises: 
 a) a hydroxy substituted benzene ring;    b) a hydroxy substituted benzene ring, wherein the benzene ring is further substituted with at least one bulky alkyl group    c) a hydroxy substituted benzene ring, wherein the benzene ring is further substituted with at least one t-butyl group;    d) a hydroxy substituted benzene ring wherein the benzene ring is further substituted with at least one t-butyl group adjacent to the hydroxy group; or    e) a hydroxy substituted benzene ring, wherein the benzene ring is further substituted with two t-butyl group wherein both t-butyl groups are adjacent to the hydroxy group.    
   
   
       6 - 9 . (canceled)  
   
   
       10 . A compound 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.  
 
   
   
       11 - 29 . (canceled)  
   
   
       30 . The compound of  claim 10 , wherein both R groups adjacent to —OH are bulkyl alkyl groups.  
   
   
       31 . The compound of  claim 10 , wherein both R groups adjacent to —OH are t-butyl.  
   
   
       32 - 38 . (canceled)  
   
   
       39 . The compound of  claim 10 , wherein n is 0, m is 1, Z is —C(O)O—, and the two R groups adjacent to the —OH are t-butyl.  
   
   
       40 . The compound of  claim 39 , wherein M is:  
     
       
         
         
             
             
         
       
     
   
   
       41 . The compound of  claim 40 , wherein 
 wherein the R 2  in the para position is —OH.    
   
   
       42 . The compound of  claim 41 , wherein  
     at least one R 2  adjacent to the para position is —OH.  
   
   
       43 . The compound of  claim 42 , wherein  
     R 2  groups in both positions adjacent to the para position are —OH.  
   
   
       44 - 45 . (canceled)  
   
   
       46 . The polymer of  claim 1 , wherein at least one of the recurring monomeric units is represented by the following structural formula:  
     
       
         
         
             
             
         
       
       wherein, independently for each occurrence: 
 n and m are integers from 0 to 18, inclusive;  
 p is an integer equal or greater than 2;  
 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 3 )O—, —OP(OR 3 )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 1  C 1-6  alkyl, —OH, —NH 2 , —SH, aryl or ester, wherein at least one R 1  is a bulky alkyl group;  
 R 2  is —H, C 1-6  alkyl, aryl, aralkyl, —OH, —NH 2 , —SH, ester or  
                     
 R 3  is —H, C 1-6  alkyl, aryl, aralkyl, heteroaryl or heteroararalkyl.  
 
     
   
   
       47 - 74 . (canceled)  
   
   
       75 . The polymer of  claim 46 , wherein: 
 n is 0;    m is 1;    Z is —C(O)O—; and    the two R groups adjacent to the —OH are t-butyl.    
   
   
       76 - 77 . (canceled)  
   
   
       78 . The polymer of  claim 75 , wherein R 2  in the para position is —OH; and the two R 2  groups adjacent to the para position are —OH.  
   
   
       79 . The polymer of  claim 1 , wherein the recurring monomeric unit is represented by the following structural formula:  
     
       
         
         
             
             
         
       
     
     wherein, independently for each occurrence: 
 n and m are integers from 0 to 18, inclusive;  
 p is an integer of at least 2;  
 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 3 )O—, —OP(OR 3 )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, —OH, —NH 2 , —SH, aryl or ester wherein at least one R 1  is a bulky alkyl group;  
 R 2  is —H, C 1-6  alkyl, aryl, aralkyl, —OH, —NH 2 , —SH or ester; and  
 R 3  is —H, C 1-6  alkyl, aryl, aralkyl, heteroaryl or heteroararalkyl.  
 
   
   
       80 - 106 . (canceled)  
   
   
       107 . The polymer of  claim 79 , wherein: 
 n is 0;    m is 1;    Z is —C(O)O—; and    the two R groups adjacent to the —OH are t-butyl.    
   
   
       108 . The polymer of  claim 107 , wherein R 2  is —H.  
   
   
       109 - 113 . (canceled)  
   
   
       114 . A method of inhibiting oxidation of a substance in an oxidizable material comprising contacting the material with: 
 a) a compound 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, 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  —H, C 1-6 alkyl, aryl, aralkyl, —OH, —NH 2 , —SH or ester; or  
   b) a polymer, wherein substantially all the monomeric units of the polymer comprise an antioxidant and wherein the polymer comprises at least one monomeric unit represented by a structural formula selected from: 
 (i)  
                     
  wherein, independently for each occurrence: 
 n and m are integers from 0 to 18, inclusive;  
 p is an integer equal or greater than 2;  
 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 35 )O—, —OP(OR 3 )O—, —C(O)OC(O)— or a bond;  
 R is —H C 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, —OH, —NH 2 , —SH, aryl or ester wherein at least one R is a bulky alkyl group;  
 R 2  is —H C 1-6  alkyl, aryl, aralkyl, —OH, —NH 2 , —SH, ester or  
                     
 R 3  is —H, C 1-6  alkyl, aryl, aralkyl, heteroaryl or heteroararalkyl; or  
 
 (ii)  
                     
  wherein, independently for each occurrence: 
 n and m are integers from 0 to 18 inclusive;  
 p is an integer of at least 2;  
 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 3 )O—, —OP(OR 3 )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, —OH, —NH 2 , —SH, aryl or ester wherein at least one R1 is a bulky alkyl group;  
 R 2  is —H, C 1-6 alkyl, aryl, aralkyl, —OH, —NH 2 , —SH or ester; and  
 R 3  is —H, C 1-6 alkyl, aryl, aralkyl, heteroaryl or heteroararalkyl.  
 
   
   
   
       115 . (canceled)  
   
   
       116 . A composition comprising: 
 a) a compound 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, 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 is —H C 6  alkyl, aryl, aralkyl, —OH, —NH 2 , —SH or ester; or  
   b) a polymer, wherein substantially all the monomeric units of the polymer comprise an antioxidant and wherein the polymer comprises at least one monomeric unit represented by a structural formula selected from:                           wherein, independently for each occurrence: 
 n and m are integers from 0 to 18, inclusive:  
 p is an integer equal or greater than 2;  
 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 3 )O—, —OP(OR 3 )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, —OH, —NH 2 , —SH, aryl or ester wherein at least one R 1  is a bulky alkyl group;  
 R 2  alkyl, aryl, aralkyl, —OH, —NH 2 , —SH, ester or  
                     
 R 3  is —H C 1-6  alkyl, aryl, aralkyl, heteroaryl or heteroararalkyl; or  
                     
    wherein, independently for each occurrence: 
 n and m are integers from 0 to 18, inclusive:  
 p is an integer of at least 2;  
 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 3 )O—, —OP(OR 3 )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, —OH, —NH 2 , —SH, aryl or ester wherein at least one R 1  is a bulky alkyl group;  
 R 2  is —H, C 1-6 alkyl, aryl, aralkyl, —OH, —NH 2 , —SH or ester; and  
 R 3  is —H, C 1-6 alkyl, aryl, aralkyl, heteroaryl or heteroararalkyl.  
 and an oxidizable material wherein the oxidizable material is an oil, food item, plastic, elastommer, petroleum product, adhesive, lubricant, paint, pigment, soap, cosmetic, metal, vitamin, pharmaceutical or packaging material.  
   
   
   
       117 . The composition of  claim 116 , wherein the oxidizable material is an oil selected from the group comprising: cottonseed oil, linseed oil, olive oil, palm oil, corn oil, peanut oil, soybean oil, castor oil, coconut oil, safflower oil, sunflower oil, canola oil and sesame oil.  
   
   
       118 . The composition of  claim 116 , wherein the oxidizable material is a food item selected from the group comprising a meat product, dairy product, cereal, beverage, cracker, potato flake, bakery product, dessert mixes, nut, candy, vegetable shortening and margarine.  
   
   
       119 . The composition of  claim 116 , wherein the oxidizable material is an elastomer selected from the group comprising a natural rubber and synthetic rubber.  
   
   
       120 . The composition of  claim 116 , wherein the oxidizable material is a petroleum product selected from the group comprising mineral oil or a fossil fuel wherein the fossil fuel is selected from the group comprising: gasoline, kerosene, diesel oil heating oil propane and jet fuel.  
   
   
       121 . The composition of  claim 116 , wherein the oxidizable material is a cosmetic selected from the group comprising a cream, lotion and hair product.  
   
   
       122 . The composition of  claim 116 , wherein the oxidizable material is a vitamin selected from the group comprising Vitamin A, Vitamin C and Vitamin E.  
   
   
       123 . The composition of  claim 116 , wherein the oxidizable material is a packaging material selected from the group comprising paper, cardboard, or a thermoplastic polymer, wherein the thermoplastic polymer is selected from the following the groups comprising: polyethylene, polypropylene, polystyrene, nylon, poly(ethylene-co-vinyl alcohol), polyethylene terephthalate, poly(vinylidene chloride) and poly(vinyl chloride).  
   
   
       124 . A The composition of  claim 116  further comprising and a non-polymer antioxidant.  
   
   
       125 . The polymer of  claim 46 , wherein the polymer comprises at least two different monomeric units.  
   
   
       126 . The polymer of  claim 46 , wherein the polymer is a random copolymer or a block copolymer.  
   
   
       127 . The polymer of  claim 79 , wherein the polymer comprises at least two different monomeric units.  
   
   
       128 . The polymer of  claim 79 , wherein the polymer is a random copolymer or a block copolymer.  
   
   
       129 . The method of  claim 114 , wherein the oxidizable material is an oil, a food item, a plastic, and elastomer, a petroleum product, an adhesive, a lubricant, a paint, a pigment, a soap, a cosmetic, a metal, a vitamin, a pharmaceutical or a packaging material.