Block copolymers for tooth enamel protection

Abstract

Described herein are block copolymers having hydrophobic blocks and hydrophilic blocks which are effective in binding to the surface of hard tissue; compositions comprising the same, as well as methods of making and using the same.

1 - 15 . (canceled) 
     
     
         16 . An oral hygienic composition comprising: an orally acceptable carrier, fluoride, and a block copolymer having at least one hydrophobic block and at least one hydrophilic block in an amount effective to bind hydroxyapatite; and wherein the oral hygienic composition is selected from the group consisting of: toothpaste, mouthwash, strips, and gel containing trays; and
 wherein the composition comprises effective amounts of fluoride, the block copolymer, and the carrier to reduce citric acid erosion of hydroxyapaptite by 15-30% as compared to the same composition without fluoride;   wherein the block copolymer has the structure of formula I or formula II:   
       
         
           
           
               
               
           
         
         where A is selected from the group consisting of (CH 2 ) p , (CH 2 CH 2 O) q , (phenyl) x , (C(═O)—O) y , (C(═O)—OCH 2 CH 2 O) b , or any combination thereof, where for substituent A p, q=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; x=0 or 1, y=0 or 1, b=0 or 1; 
         R 1  is selected from the group consisting of H a , (CH 2 ) p , (CH 2 CH 2 O) q , (phenyl) x , (C(═O)—O) y , (C(═O)—OH) c , (C(═O)—OCH 3 ) d , (C(═O)—OCH(CH 3 ) 3 ) e  or any combination thereof, where for R 1  p, q=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; x=0 or 1, y=0 or 1, a=0 or 1, c=0 or 1, d=0 or 1, e=0 or 1; 
         R 2  is selected from the group consisting of H a , (CH 2 ) p , (CH 2 CH 2 O) q , (phenyl) x , (C(═O)—O) y , (C(═O)—OH) c , (C(═O)—OCH 3 ) d , (C(═O)—OCH(CH 3 ) 3 ) e , or any combination thereof, where for R 2  p, q=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; x=0 or 1, y=0 or 1, a=0 or 1, c=0 or 1, d=0 or 1, e=0 or 1; 
         R 3  is selected from the group consisting of H a , (CH 2 ) p , (CH 2 CH 2 O) q , (phenyl) x , (C(═O)—O) y , (C(═O)—OH) c , (C(═O)—OCH 3 ) d , (C(═O)—OCH(CH 3 ) 3 ) e , or any combination thereof, where for R 3  p, q=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; x=0 or 1, y=0 or 1, a=0 or 1, c=0 or 1, d=0 or 1, e=0 or 1; 
         R 4  is selected from the group consisting of H a , (CH 2 ) p , (CH 2 CH 2 O) q , (phenyl) x , (C(═O)—O) y , (C(═O)—OH) c , (C(═O)—OCH 3 ) d , (C(═O)—OCH(CH 3 ) 3 ) e , or any combination thereof, where for 
         R 4  p, q=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; x=0 or 1, y=0 or 1, a=0 or 1, c=0 or 1, d=0 or 1, e=0 or 1; 
         R 5  is selected from the group consisting of H a , (CH 2 ) p , (CH 2 CH 2 O) q , (phenyl) x , (C(═O)—O) y , (C(═O)—OH) c , (C(═O)—OCH 3 ) d , (C(═O)—OCH(CH 3 ) 3 ) e , or any combination thereof, where for 
         R 5  p, q=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; x=0 or 1, y=0 or 1, a=0 or 1, c=0 or 1, d=0 or 1, e=0 or 1; 
         R 6  is selected from the group consisting of H a , (CH 2 ) p , (CH 2 CH 2 O) q , (phenyl) x , (C(═O)—O) y , (C(═O)—OH) c , (C(═O)—OCH 3 ) d , (C(═O)—OCH(CH 3 ) 3 ) e , or any combination thereof, where for 
         R 6  p, q=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; x=0 or 1, y=0 or 1, a=0 or 1 or c=0 or 1, d=0 or 1, e=0 or 1; 
         R 7  is selected from the group consisting of H a , (CH 2 ) p , (CH 2 CH 2 O) q , (phenyl) x , (C(═O)—O) y , (C(═O)—OH) c , (C(═O)—OCH 3 ) d , (C(═O)—OCH(CH 3 ) 3 ) e , or any combination thereof, where for 
         R 7  p, q=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; x=0 or 1, y=0 or 1, a=0 or 1, c=0 or 1, d=0 or 1, e=0 or 1; 
         R 8  is selected from the group consisting of an alkali metal, an ammonium, protonated alkyl amine, H a , (CH 2 ) p , (CH 2 CH 2 O) q , (phenyl) x , (C(═O)—O) y , or any combination thereof, where for 
         R 8  p, q=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; x=0 or 1, y=0 or 1, a=0 or 1; 
         R 9  is selected from the group consisting of an alkali metal, an ammonium, protonated alkyl amine, H a , (CH 2 ) p , (CH 2 CH 2 O) q , (phenyl) x , (C(═O)—O) y , or any combination thereof, where for 
         R 9  p, q=0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; x=0 or 1, y=0 or 1, a=0 or 1; 
         R 10  is hydrogen, methyl, alkali metal or ammonium; and 
         m and n are each independently in a range from about 5 to about 3000. 
       
     
     
         17 . The composition of  claim 16 , wherein the block copolymer is selected from the group consisting of a poly methyl methacrylate-poly methacryloyloxyethyl phosphate block copolymer, a poly methyl methacrylate-poly acrylate acid block copolymer, and a poly methyl methacrylate-poly tert-butyl acrylate block copolymer. 
     
     
         18 . (canceled) 
     
     
         19 . (canceled) 
     
     
         20 . The composition of  claim 16 , wherein n is from 5 to 400 and wherein m is from 5 to 100. 
     
     
         21 . A method for protecting tooth enamel from acid erosion, the method comprising:
 applying a block copolymer according to  claim 16  to tooth enamel.   
     
     
         22 . The method of  claim 21 , wherein the block copolymer is effective to protect the hydroxyapatite from loss of calcium by at least about 10 percent after exposure of the hydroxyapatite to the copolymer and subsequent exposure of the copolymer coated hydroxyapatite to citric acid. 
     
     
         23 . The method of  claim 21 , wherein the block copolymer has a molecular weight in a range of from about 1,000 to have 1,000,000. 
     
     
         24 . The method of  claim 21 , wherein the block copolymer has a molecular weight in the range of from about 1,000 to about 1,000,000, individual hydrophilic blocks having a molecular weight in the range of from about 200 to about 1,000,000, and individual hydrophobic blocks having a molecular weight in the range of from about 200 to about 1,000,000. 
     
     
         25 . The method of  claim 21 , wherein the hydrophilic blocks comprise from about 10 to about 90 weight percent of the block copolymer and the hydrophobic blocks comprise from about 10 to about 90 weight percent of the block copolymer. 
     
     
         26 . (canceled) 
     
     
         27 . The method  claim 21 , wherein the block copolymer is selected from the group consisting of a poly methyl methacrylate-poly methacryloyloxyethyl phosphate block copolymer, a poly methyl methacrylate-poly acrylate acid block copolymer, and a poly methyl methacrylate-poly tert-butyl acrylate block copolymer. 
     
     
         28 . (canceled) 
     
     
         29 . The method of  claim 21 , wherein the tooth enamel is exposed to a citric acid solution before and/or after applying the block copolymer. 
     
     
         30 . The method of  claim 26 , wherein n is from 5 to 400 and wherein m is from 5 to 100.