Stabilizers for polymerizable biocompatible materials

Abstract

The present invention provides polymerizable biocompatible materials stabilized by amino acids or reducing salts to improve shelf life. Methods of stabilizing a polymerizable biocompatible material are also provided that inhibit auto polmerization of the material over time.

1 . A polymerizable biocompatible material comprising a stabilizing amount of amino acid.  
     
     
         2 . The polymerizable biocompatible material of  claim 1  wherein the amino acid is cysteine, cystine, arginine, or proline.  
     
     
         3 . The polymerizable biocompatible material of  claim 1  wherein the amino acid is an L-amino acid.  
     
     
         4 . The polymerizable biocompatible material of  claim 1  wherein the amino acid is L-cysteine.  
     
     
         5 . The polymerizable biocompatible material of  claim 1  wherein the stabilizing amount is 0.1%-10% by weight of the polymerizable biocompatible material.  
     
     
         6 . The polymerizable biocompatible material of  claim 1  wherein the stabilizing amount is 0.3%-5% by weight of the polymerizable biocompatible material.  
     
     
         7 . The polymerizable biocompatible material of  claim 1  wherein the stabilizing amount is 0.3%-5% by weight of the polymerizable biocompatible material.  
     
     
         8 . The polymerizable biocompatible material of  claim 1  wherein said biocompatible material comprises at least one monomer having an acrylic functional group.  
     
     
         9 . The polymerizable biocompatible material of  claim 8  wherein said monomer is bisphenol-A-diglycidyl methacrylate, triethyleneglycol dimethacrylate, diurethane dimethacrylate, bisphenol-A-ethoxy methacrylate, methylmethacrylate, or methacrylate.  
     
     
         10 . The polymerizable biocompatible material of  claim 9  wherein said biocompatible material comprises at least one ethylenically unsaturated monomer.  
     
     
         11 . The polymerizable biocompatible material of  claim 1  wherein said biocompatible material further comprises a filler comprised of particles ranging from about 0.01 μm to 2-3 mm.  
     
     
         12 . The polymerizable biocompatible material of  claim 1  wherein said particles range from about 0.1 to 100 μm.  
     
     
         13 . The polymerizable biocompatible material of  claim 11  wherein said filler is bioactive.  
     
     
         14 . The polymerizable biocompatible material of  claim 1  further comprising a polymerization inhibitor, wherein said inhibitor is hydroquinone or a functional equivalent.  
     
     
         15 . The polymerizable biocompatible material of  claim 14  wherein said polymerization inhibitor, is butylatedhydroxytoluene, butylated hydroxyaniline, UV-9 (2-hydroxy-4-methoxy benzophenone), methyl ether hydroquinone, 4-benzyloxy phenol, or 3,5-diisopropyl phenol.  
     
     
         16 . The polymerizable biocompatible material of  claim 15  wherein the polymerization inhibitor is butylatedhydroxytoluene.  
     
     
         17 . The polymerizable biocompatible material of  claim 1  wherein the material forms a liquid/powder or paste/paste system.  
     
     
         18 . A polymerizable biocompatible material comprising a stabilizing amount of reducing salt.  
     
     
         19 . The polymerizable biocompatible material of  claim 18  wherein the reducing salt is sodium thiosulfate, iron sulfate, or sodium hypophospite.  
     
     
         20 . The polymerizable biocompatible material of  claim 18  wherein the stabilizing amount is 0.1%-10% by weight of the polymerizable biocompatible material.  
     
     
         21 . The polymerizable biocompatible material of  claim 18  wherein the stabilizing amount is 0.3%-5% by weight of the polymerizable biocompatible material.  
     
     
         22 . The polymerizable biocompatible material of  claim 18  wherein the stabilizing amount is 0.3%-1% by weight of the polymerizable biocompatible material.  
     
     
         23 . The polymerizable biocompatible material of  claim 18  wherein said biocompatible material comprises at least one monomer having an acrylic functional group.  
     
     
         24 . The polymerizable biocompatible material of  claim 23  wherein said monomer is bisphenol-A-diglycidyl methacrylate, triethyleneglycol dimethacrylate, diurethane dimethacrylate, bisphenol-A-ethoxy methacrylate, methylmethacrylate, or methacrylate.  
     
     
         25 . The polymerizable biocompatible material of  claim 24  wherein said biocompatible material comprises at least one ethylenically unsaturated monomer.  
     
     
         26 . The polymerizable biocompatible material of  claim 18  wherein said biocompatible material further comprises a filler comprised of particles ranging from about 0.01 μm to 2-3 mm.  
     
     
         27 . The polymerizable biocompatible material of  claim 26  wherein said particles range from about 0.1 to 100 μm.  
     
     
         28 . The polymerizable biocompatible material of  claim 26  wherein said filler is bioactive.  
     
     
         29 . The polymerizable biocompatible material of  claim 18  further comprising a polymerization inhibitor, wherein said inhibitor is hydroquinone or a functional equivalent.  
     
     
         30 . The polymerizable biocompatible material of  claim 29  wherein said polymerization inhibitors, is butylatedhydroxytoluene, butylated hydroxyaniline, UV-9 (2-hydroxy-4-methoxy benzophenone), methyl ether hydroquinone, 4-benzyloxy phenol, or 3,5-diisopropyl phenol.  
     
     
         31 . The polymerizable biocompatible material of  claim 30  wherein the polymerization inhibitor is butylatedhydroxytoluene.  
     
     
         32 . The polymerizable biocompatible material of  claim 18  wherein the material forms a liquid/powder or paste/paste system.  
     
     
         33 . A method of stabilizing a polymerizable biocompatible material comprising: 
 providing at least one monomer having an acrylate functional group,    adding a stabilizing amount of an amino acid to said monomer to form a stabilizing mix, and    adding a filler to said mix to form a stabilized paste.    
     
     
         34 . The method of  claim 33  wherein said amino acid is cysteine,cystine, arginine, or proline.  
     
     
         35 . The method of  claim 33  wherein said amino acid is an L-amino acid.  
     
     
         36 . The method of  claim 33  wherein said amino acid is L-cysteine.  
     
     
         37 . The method of  claim 33  wherein the stabilizing amount is 0.1%-10% by weight of the polymerizable biocompatible material.  
     
     
         38 . The method of  claim 33  wherein the stabilizing amount is 0.3%-5% by weight of the polymerizable biocompatible material.  
     
     
         39 . The method of  claim 33  wherein the stabilizing amount is 0.3%-1% by weight of the polymerizable biocompatible material.  
     
     
         40 . The method of  claim 33  wherein said biocompatible material comprises at least one monomer having an acrylic functional group.  
     
     
         41 . The method of  claim 40  wherein said monomer is bisphenol-A-diglycidyl methacrylate, triethyleneglycol dimethacrylate, diurethane dimethacrylate, bisphenol-A-ethoxy methacrylate, methylmethacrylate, or methacrylate.  
     
     
         42 . The method of  claim 41  wherein said monomer is an ethylenically unsaturated monomer.  
     
     
         43 . The method of  claim 33  wherein said biocompatible material further comprises a filler comprised of particles ranging from about 0.01 μm to 2-3 mm.  
     
     
         44 . The method of  claim 33  wherein said particles range from about 0.1 to 100 μm.  
     
     
         45 . The method of  claim 33  wherein said filler is bioactive.  
     
     
         46 . The method of  claim 33  further comprising polymerization inhibitors is hydroquinone or various functional equivalents.  
     
     
         47 . The method of  claim 46  wherein said functional equivalents are butylatedhydroxytoluene, butylated hydroxyaniline, UV-9 (2-hydroxy-4-methoxy benzophenone), methyl ether hydroquinone, 4-benzyloxy phenol, or 3,5-diisopropyl phenol.  
     
     
         48 . The method of  claim 47  wherein the polymerization inhibitor is butylatedhydroxytoluene.  
     
     
         49 . A method of stabilizing a polymerizable biocompatible material comprising: 
 providing at least one monomer having an acrylate functional group,    adding a stabilizing amount of a reducing salt to said monomer to form a stabilizing mix, and    adding a filler to said mix to form a stabilized paste.    
     
     
         50 . The method of  claim 49  wherein said reducing salt is sodium thiosulfate, iron sulfate, or sodium hypophospite.  
     
     
         51 . The method of  claim 49  wherein the stabilizing amount is 0.1%-10% by weight of the polymerizable biocompatible material.  
     
     
         52 . The method of  claim 49  wherein the stabilizing amount is 0.3%-5% by weight of the polymerizable biocompatible material.  
     
     
         53 . The method of  claim 49  wherein the stabilizing amount is 0.3%-1% by weight of the polymerizable biocompatible material.  
     
     
         54 . The method of  claim 49  wherein said material comprises at least one monomer having an acrylic functional group.  
     
     
         55 . The method of  claim 54  wherein said monomer is bisphenol-A-diglycidyl methacrylate, triethyleneglycol dimethacrylate, diurethane dimethacrylate, bisphenol-A-ethoxy methacrylate, methylmethacrylate, or methacrylate.  
     
     
         56 . The method of  claim 55  wherein said monomer is an ethylenically unsaturated monomer.  
     
     
         57 . The method of  claim 49  wherein said material comprises a filler comprised of particles ranging from about 0.01 μm to 2-3 mm.  
     
     
         58 . The method of  claim 49  wherein said particles range from about 0.1 to 100 μm.  
     
     
         59 . The method of  claim 57  wherein said filler is bioactive.  
     
     
         60 . The method of  claim 49  further comprising polymerization inhibitors is hydroquinone or various functional equivalents.  
     
     
         61 . The method of  claim 60  wherein said functional equivalents are butylatedhydroxytoluene, butylated hydroxyaniline, UV-9 (2-hydroxy-4-methoxy benzophenone), methyl ether hydroquinone, 4-benzyloxy phenol, or 3,5-diisopropyl phenol.  
     
     
         62 . The method of  claim 61  wherein the polymerization inhibitor is butylatedhydroxytoluene.