Self-healing dental restorative formulations and related methods

1. A dental restorative formulation, comprising:

a first capsule consisting of a radical initiator within said first capsule; and

a second capsule consisting of one or more monomers and a radical accelerator within said second capsule,

the dental restorative formulation is polymerized to form a composite and upon the occurrence of a disturbance in the composite said first capsule and said second capsule rupture such that said radical accelerator of said second capsule decomposes said radical initiator of said first capsule to polymerize said one or more monomers of said second capsule thereby healing the composite.

2. The dental restorative formulation of claim 1 , wherein said radical initiator is an organic peroxide initiator.

3. The dental restorative formulation of claim 1 , wherein said radical initiator is benzoyl peroxide.

4. The dental restorative formulation of claim 1 , wherein said one or more monomers is acrylic monomers.

5. The dental restorative formulation of claim 1 , wherein said one or more monomers is triethyleneglycol dimethacrylate (“TEGDMA”).

6. The dental restorative formulation of claim 1 , wherein said one or more monomers is 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (“Bis-GMA”).

7. The dental restorative formulation of claim 1 , wherein said one or more monomers is 2,2,4-trimethylhexamethylene diurethane (“UDMA”).

8. The dental restorative formulation of claim 1 , wherein said radical accelerator is N,N-dimethyl-p-toluidine.

9. The dental restorative formulation of claim 1 , wherein said one or more monomers are selected from the group consisting of: 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy) phenyl]propane (“Bis-GMA”), dimethacryloxyethyl 2,2,4-trimethylhexamethylene diurethane (“UDMA”), and 1,6-bis-[2-methacryloxy-ethoxycarbonylamino]-2,2,4-trimethylhexane (“UEDMA”), triethyleneglycol dimethacrylate (“TEGDMA”), polyethylene glycol dimethacrylate (“PEGDMA”), glyceroldimethacrylate (“GDM”), methacryloyloxyethyl maleate (“MEMA”), diethyleneglycol dimethacrylate (“DEGDMA”), hexanediol dimethacrylate (“HDMA”), hexanediol diacrylate (“HDDA”), trimethylolpropanetriacrylate (“TMPTA”), trimethylolpropanetrimethacrylate (“TMPTMA”), ethoxylated trimethylolpropanetriacrylate (“EOTMPTA”), hydroxyethyl methacrylate (“HEMA”) and ethoxylated bisphenol A dimethacrylate (“EBPADMA”), isopropyl methacrylate; n-hexyl acrylate; stearyl acrylate; diallyl phthalate; divinyl succinate; divinyl adipate: divinyl phthalate; allyl acrylate; glycerol triacrylate; ethyleneglycol diacrylate; 1,3-propanediol di(meth)acrylate; decanediol dimethacrylate; 1,12-dodecanediol di(meth)acrylate; trimethylolpropane mono- or di-(meth)acrylate; trimethylolpropane triacrylate; butanediol di(meth)acrylate; 1,2,4-butanetriol trimethacrylate: 1,4-cyclohexanediol diacrylate; pentaerythritol tetra(meth)acrylate; sorbitol mono-, di-, tri-, tetra-, or penta-(meth)acrylate; sorbitol hexa-(meth)acrylate; tetrahydrofurfuiryl (meth)acrylate; bis[1-(2-acryloxy)]-p-ethoxyphenyldimethylmethane; bis[1-(3-acryloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane; 2,2,4-trimethylhexamethylene diisocyanate; tris-hydroxyethyl-isocyanurate trimethacrylate, glycerol phosphate monomethacrylates; glycerol phosphate dimethacrylates; hydroxyethyl methacrylate phosphates; 2-hydroxypropyl(meth)acrylate; citric acid di- or tri-methacrylates; fluoropolymer-functional (meth)acrylates; poly(meth)acrylated polymaleic acid; poly(meth)acrylated polycarboxyl-polyphosphonic acid; poly(meth)acrylated polychlorophosphoric acid; poly(meth)acrylated polysulfonic acid; poly(meth)acrylated polyboric acid; polymerizable bisphosphonic acids, and siloxane-functional (meth)acrylate polysiloxanes, defined as products resulting from hydrolytic polycondensation of one or more of the following silanes: bis[2-(2-(methacryloyl oxyethoxycarbonyl)ethyl)]-3-triethoxysily-lpropyl amine, bis[2-(2(1)-(methacryloyloxypropoxycarbonyl)ethyl)]-3-triet-hoxysilylpropyl amine, 1,3(2)-dimethacryloyloxypropyl-[3-(3-triethoxysilyl-propyl)aminocarbonyl]propionate, 1,3(2)-dimethacryloyloxypropyl-[4-(3-trie-thoxysilylpropyl)aminocarbonyl]butyrate, 1,3(2)-dimethacryloyloxypropyl-[-4-(3-triethoxysilylpropyl)-N-ethylaminocarbonyl]butyrate, 3-[1,3(2)-dimethacryloyl oxypropyl)-2(3)-oxycarbonylamido]-propyltriethoxysilane, glycerol phosphate monomethacrylates, glycerol phosphate dimethacrylates, hydroxyethyl methacrylate phosphates, citric acid di- or tri-methacrylates, poly(meth)acrylated oligomaleic acid, poly(meth)acrylated polymaleic acid, poly(meth)acrylated poly(meth)acrylic acid, poly(meth)acrylated polycarboxyl-polyphosphonic acid, poly(meth)acrylated polychlorophosphoric acid, poly(meth)acrylated polysulfonic acid, poly(meth)acrylated polyboric acid and polymerizable bisphosphonic acids.

10. The dental restorative formulation of claim 1 , wherein said radical accelerator includes one or more amines selected from the group consisting of: dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, n-propyl amine, di-n-propyl amine, tri-n-propyl amine, isopropyl amine, diisopropyl amine, triisopropyl amine, n-butyl amine, isobutyl amine, t-butyl amine, di-n-butyl amine, diisobutyl amine, tri-isobutyl amine, pentyl amine, isopentyl amine, diisopentyl amine, hexyl amine, octyl amine, dodecyl amine, lauryl amine, stearyl amine, aminoethanol, diethanol amine, triethanol amine, aminohexanol, ethoxy aminoethane, dimethyl-(2-chloroethyl) amine, 2-ethylhexyl amine, bis-(2-chloroethyl) amine, 2-ethylhexyl amine, bis-(2-ethylhexyl) amine, N-methyl stearylamine, dialkyl amines, ethylene diamine, N,N′-dimethyl ethylene diamine, tetramethyl ethylene diamine, diethylene triamine, permethyl diethylene triamine, triethylene tetramine, tetraethylene pentamine, 1,2-diaminopropane, di-propylene triamine, tripropylene tetramine, 1,4-diamino butane, 1,6-diamino hexane, 4-amino-1-diethyl aminopentane, 2,5-diamino-2,5-dimethyl hexane, trimethyl hexamethylene diamine, N,N-dimethyl aminoethanol, 2-(2-diethylamino ethoxy) ethanol, bis-(2-hydroxyethyl)-oleyl amine, tris-[2-(2-hydroxy-ethoxy)-ethyl]amine, 3-amino-1-propanol, methyl-(3-aminopropyl)ether, ethyl-(3-aminopropyl)ether, 1,4-butane diol-bis(3-aminopropyl ether), 3-dimethylamino-1-propanol, 1-amino-2-propanol, 1-diethylamino-2-propanol, diisopropanol amine, methyl-bis-(2-hydroxypropyl)-amine, tris-(2-hydroxypropyl) amine, 4-amino-2-butanol, 2-amino-2-methylpropanol, 2-amino-2-methyl-propanediol, 2-amino-2-hydroxymethylpropanediol, 5-diethylamino-2-pentanone, 3-methylaminopropionic acid nitrile, 6-aminohexanoic acid, 11-aminoundecanoic acid, 6-aminohexanoic acid ethyl ester, 11-aminohexanoic acid isopropyl ester, cyclohexyl amine, N-methylcyclohexyl amine, N,N-dimethylcyclohexyl amine, dicyclohexyl amine, N-ethylcyclohexyl amine, N-(2-hydroxyethyl)-cyclohexyl amine, N,N-bis-(2-hydroxyethyl)-cyclohexyl amine, N-(3-aminopropyl)-cyclohexyl amine, aminomethyl cyclohexane, hexahydro toluidine, hexahydro benzylamine, aniline, N-methyl aniline, N,N-dimethyl aniline, N,N-diethyl aniline, N,N-di-propyl aniline, isobutyl aniline, toluidines, diphenyl amine, hydroxyethyl aniline, bis-(hydroxyethyl) aniline, chloro-aniline, aminophenols, aminobenzoic acids and their esters, benzyl amine, dibenzyl amine, tribenzyl amine, methyldibenzyl amine, a-phenylethyl amine, xylidine, diisopropyl aniline, dodecyl aniline, amino naphthalene, N-methyl aminonaphthalene, N,N-dimethyl aminonaphthalene, N,N-dibenzyl naphthalene, diamine cyclohexane, 4,4′-diamino-dicyclohexyl methane, diamino-dimethyl-dicyclohexyl methane, phenylene diamine, xylylene diamine, diamine biphenyl, naphthalene diamines, toluidines, benzidines, 2,2-bis-(aminophenyl)-propane, amino anisoles, amino-thiophenols, aminodiphenyl ethers, amino cresols, morpholine, N-methyl morpholine, N-phenyl morpholine, hydroxyethyl morpholine, N-methyl pyrrolidine, pyrrolidine, piperidine, hydroxyethyl piperidine, pyrrols, pyridines, chinolines, indoles, indolenines, carbazoles, pyrazoles, imidazoles, thiazoles, pyrimidines, chinoxalines, amino morpholine, dimorpholine ethane, [2,2,2]-diazabicyclo octane, and N,N-dimethyl-p-toluidine.

11. The dental restorative formulation of claim 1 , wherein said radical initiator is one or more selected from the group consisting of: azo compounds, inorganic peroxides, acetophenone, benzil/benzoin, redox, ylide, benzophenone, thioxanthones and organic peroxides.

12. The dental restorative formulation of claim 1 , wherein the said first capsule and said second capsule account for about 1-15 wt % of the dental composite.

13. A method of forming a dental composite including a dental restorative formulation, comprising the steps of:

providing a dental material;

adding a first capsule to the dental material, wherein the first capsule consists of a radical initiator within the first capsule;

introducing a second capsule to the dental material, wherein the second capsule consists of one or more monomers and a radical accelerator within the second capsule;

applying the dental material including the first capsule additive and the second capsule and

polymerizing the dental material to form a dental composite,

wherein a rupturing of the first capsule and the second capsule when a disturbance occurs in the dental composite causes the radical accelerator of the second capsule to decompose the radical initiator of the first capsule to polymerize the one or more monomers of the second capsule thereby healing the disturbance in the dental composite.