Polymerizable compositions containing salts of barbituric acid derivatives

Abstract

This invention relates to polymerizable compositions comprising a salt of a barbituric acid derivative. The compositions are typically shelf-life stable and may be polymerized through mixing of an acidic component with the salt of a barbituric acid derivative.

1 . A free-radically polymerizable composition comprising:
 a. a compound having the general formula (I)   
       
         
           
           
               
               
           
         
         
           wherein R1, R2, and R3 are independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, cycloalkyl, substituted cycloalkyl, arylalkyl, aryl or substituted aryl; 
           X is oxygen or sulfur; 
           Y is a metal cation or organic cation; and 
         
         b. an ethylenically unsaturated compound without acid functionality. 
       
     
     
         2 . A free-radically polymerizable composition comprising:
 a. a salt of barbituric acid, thiobarbituric acid, barbituric acid derivative, or thiobarbituric acid derivative, and   b. an ethylenically unsaturated compound without acid functionality.   
     
     
         3 . The composition of  claim 1 , wherein components (a) and (b) form a stable mixture when mixed together. 
     
     
         4 . The composition of  claim 2 , wherein the salt comprises an inorganic cation. 
     
     
         5 . The composition of  claim 4 , wherein the inorganic cation comprises a metal M that is able to provide stable cations M + , M 2+ , or M 3+ . 
     
     
         6 . The composition of  claim 4 , wherein the inorganic cation is a cation of Li, Na, K, Mg, Ca, Sr, Ba, Al, Fe, Cu, Zn, or La. 
     
     
         7 . The composition of  claim 4 , wherein the cation is a cation of Na, K, or Ca. 
     
     
         8 . The composition of  claim 2 , wherein the salt of barbituric acid comprises the calcium salt of 1-benzyl-5-phenyl-barbituric acid or sodium salt of 1-benzyl-5-phenyl-barbituric acid. 
     
     
         9 . The composition of  claim 2 , wherein the salt of thiobarbituric acid comprises the calcium salt of 5-phenyl-thiobarbituric acid. 
     
     
         10 . The composition of  claim 2 , wherein the salt comprises an organic cation. 
     
     
         11 . The composition of  claim 10 , wherein the organic cation is a cation of ammonium, alkylammonium, or triethanolammonium. 
     
     
         12 . The composition of  claim 2 , wherein the salt of barbituric acid comprises the triethanolammonium salt of 1-benzyl-5-phenyl-barbituric acid. 
     
     
         13 . The composition of  claim 1 , further comprising an acidic component. 
     
     
         14 . The composition of  claim 1 , further comprising a precursor of an acidic component. 
     
     
         15 . The composition of  claim 13 , wherein the acidic component or precursor of acidic component is an ethylenically unsaturated compound. 
     
     
         16 . The composition of  claim 13 , wherein the composition has been cured by mixing the acidic component, the salt compound, and the ethylenically unsaturated compound without acid functionality. 
     
     
         17 . The composition of  claim 15 , wherein the ethylenically unsaturated compound with acid functionality is 1,3-glycerol dimethacrylate phosphate. 
     
     
         18 . The composition of  claim 13 , wherein the acidic component or precursor of an acidic component has a pKa lower than that of the barbituric acid, thiobarbituric acid, barbituric acid derivative or thiobarbituric acid derivative used for the synthesis of the compound having the general formula (I). 
     
     
         19 . The composition of  claim 13 , wherein the acidic component or precursor of an acidic component cures the composition. 
     
     
         20 . The composition of  claim 1 , wherein the ethylenically unsaturated compound without acid functionality comprises an acrylate or a methacrylate. 
     
     
         21 . The composition of  claim 1 , wherein the ethylenically unsaturated compound without acid functionality is triethyleneglycol dimethacrylate or propoxylated Bisphenol A dimethacrylate. 
     
     
         22 . The composition of  claim 1 , wherein the salt compound comprises the calcium salt of 1-benzyl-5-phenyl-barbituric acid, the sodium salt of 1-benzyl-5-phenyl-barbituric acid, the triethanolammonium salt of 1-benzyl-5-phenyl-barbituric acid, or the calcium salt of 5-phenyl-thiobarbituric acid, and the ethylenically unsaturated compound without acid functionality comprises a mixture of triethyleneglycol dimethacrylate or propoxylated Bisphenol A dimethacrylate. 
     
     
         23 . The composition of  claim 22 , further comprising 1,3-glycerol dimethacrylate phosphate. 
     
     
         24 . The composition of  claim 1 , further comprising an additive selected from the group consisting of a water adsorbent, a fumed silica, an accelerator, a pigment, a photoinitiator system, a redox cure system and a stabilizer. 
     
     
         25 . The composition of  claim 1 , further comprising a filler. 
     
     
         26 . A kit comprising the free-radically polymerizable composition of  claim 1 , a composition comprising an acidic compound or precursor to an acidic compound, and means for mixing. 
     
     
         27 . The kit of  claim 26 , wherein the acidic compound is an ethylenically unsaturated compound with acid functionality. 
     
     
         28 . The kit of  claim 27 , wherein the ethylenically unsaturated compound with acid functionality is 1,3-glycerol dimethacrylate phosphate. 
     
     
         29 . The kit of  claim 26 , wherein the ethylenically unsaturated compound without acid functionality is a methacrylate. 
     
     
         30 . The kit of  claim 29 , wherein the methacrylate is triethyleneglycol dimethacrylate, propoxylated Bisphenol A dimethacrylate, or a mixture of triethyleneglycol dimethacrylate and propoxylated Bisphenol A dimethacrylate. 
     
     
         31 . The kit of  claim 26 , wherein the salt compound or the compound having the general formula (I) comprises the calcium salt of 1-benzyl-5-phenyl-barbituric acid, the sodium salt of 1-benzyl-5-phenyl-barbituric acid, the triethanolammonium salt of 1-benzyl-5-phenyl-barbituric acid, or the calcium salt of 5-phenyl-thiobarbituric acid. 
     
     
         32 . The kit of  claim 26 , wherein the salt compound or the compound having the general formula (I) comprises the calcium salt of 1-benzyl-5-phenyl-barbituric acid, the sodium salt of 1-benzyl-5-phenyl-barbituric acid, the triethanolammonium salt of 1-benzyl-5-phenyl-barbituric acid, or the calcium salt of 5-phenyl-thiobarbituric acid, and the ethylenically unsaturated compound without acid functionality comprises a mixture of triethyleneglycol dimethacrylate and propoxylated Bisphenol A dimethacrylate. 
     
     
         33 . The kit of  claim 32 , wherein the acidic component is 1,3-glycerol dimethacrylate phosphate. 
     
     
         34 . A method for curing a dental formulation comprising:
 a. preparing the composition according to  claim 1 ,   b. preparing a composition comprising a compound selected from the group consisting of an ethylenically unsaturated compound with acid functionality, an acidic component, or a precursor of an acidic component, and   c. mixing together the composition of (a) and the composition of (b).   
     
     
         35 . The method of  claim 34 , wherein the amount of acid is such that mixing converts some of the salt compound into a form that is not a salt. 
     
     
         36 . A redox initiator system comprising:
 a. a salt of barbituric acid, thiobarbituric acid, barbituric acid derivative, or thiobarbituric acid derivative,   b. an acidic compound, and   c. a copper compound   
     
     
         37 . The redox initiator system of  claim 36 , wherein component (a) has the following structure: 
       
         
           
           
               
               
           
         
         wherein R1, R2, and R3 are independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, cycloalkyl, substituted cycloalkyl, arylalkyl, aryl or substituted aryl; 
         X is oxygen or sulfur; and 
         Y is a metal cation or organic cation. 
       
     
     
         38 . The composition of  claim 2 , wherein the salt of barbituric acid, thiobarbituric acid, barbituric acid derivative, or thiobarbituric acid derivative comprise an organic cation or a metal cation. 
     
     
         39 . The composition of  claim 1 , wherein the organic cation is ammonium cation or alkylammonium cation. 
     
     
         40 . The composition of  claim 1 , wherein the metal cation is a metal M able to provide stable cations M + , M 2+ , or M 3+ . 
     
     
         41 . The composition of  claim 1 , wherein the metal cation is the cation of Li, Na, K, Mg, Ca, Sr, Ba, Al, Fe, Cu, Zn, or La. 
     
     
         42 . The composition of  claim 1 , wherein the metal cation is the cation of Na, K, or Ca. 
     
     
         43 . The composition of  claim 1 , wherein the metal cation is the cation of Ca. 
     
     
         44 . The composition of  claim 1 , wherein the organic cation comprises a cation of ammonium or alkylammonium. 
     
     
         45 . The compositions of  claim 1 , wherein the free-radically polymerizable composition is used as part of a coatings composition.