Dental resins, dental composite materials, and method of manufacture thereof

1. A polymerizable dental restorative composition, comprising

a resin composition comprising an oligomer comprising units having the structure:

AB  (I)

wherein A is an organic radical comprising 1 to about 6 (meth)acrylate groups and 0 to about 5 hydroxy groups; and B is an organic radical comprising 1 to about 5 epoxide groups, wherein A and B are linked through the reaction of an epoxide and a hydroxy group; and

a filler composition comprising

a polyhedral oligomeric silsesquioxane filler; and

a sol-derived filler.

2. The polymerizable dental restorative composition of claim 1 , wherein the ratio of total epoxide groups to (meth)acrylate groups is about 1:10 to about 10:1.

3. The polymerizable dental restorative composition of claim 1 , wherein the resin comprises the reaction product of a hydroxy (meth)acrylate of the formula

wherein m and n are independently 1 to 6; M is a substituted or unsubstituted C 1 -C 33 alkyl or aryl group; and R is hydrogen or methyl; and

a multifunctional epoxide of the formula

wherein E is a substituted or unsubstituted alkyl, alkoxy, alkylether, heterocycle, alkaryl, or aryl group, and x is 2 to about 6.

4. The polymerizable dental restorative composition of claim 3 , wherein the multifunctional epoxide is

wherein Y is a divalent C 1 -C 33 substituted or unsubstituted alkyl, alkoxy, aryl, alkylether, heterocycle, or alkaryl group, and q is 0 to about 20.

5. The polymerizable dental resin of claim 4 , wherein the multifunctional epoxide is

wherein X is oxygen, sulfur, carbonyl, or a divalent C 1 -C 6 alkyl, alkylether, or aryl group, d is 1 to about 4, and i is 0 to about 6.

6. The polymerizable dental resin composition of claim 5 , wherein q is 0; m is 1; X is —CH 2 — or —C(CH 3 ) 2 —; i is 1; Q is hydrogen or bromine; and M is a divalent linear C 2 -C 4 alkyl group.

7. The polymerizable dental resin composition of claim 6 , wherein q is 0; m is 1; X is CH 2 or C(CH 3 ) 2 ; i is 1; Q is hydrogen; and M is —CH 2 CH 2 — or —(CH 2 ) 4 CO 2 (CH 2 ) 2 —.

8. The polymerizable dental resin composition of claim 7 , wherein q is 0; m is 1; X is C(CH 3 ) 2 ; i is 1; Q is hydrogen; and M is —CH 2 CH 2 —.

9. The polymerizable dental resin composition of claim 1 , wherein the reaction product comprises a compound having the structure:

wherein Y is a divalent C 1 -C 33 substituted or unsubstituted alkyl, alkoxy, aryl, alkylether, heterocyclic, or alkaryl group; M is a substituted or unsubstituted C 1 -C 33 alkyl or aryl group; R is hydrogen or methyl; and q is 0 to about 20.

10. The polymerizable dental restorative composition of claim 9 , wherein q is 0 and Y is derived from bisphenol A.

11. The polymerizable dental restorative composition of claim 10 , wherein M is a divalent C 2 -C 4 alkyl group.

12. The polymerizable dental restorative composition of claim 1 , wherein the resin composition has a volume shrinkage of less than about 8% after curing.

13. The polymerizable dental restorative composition of claim 1 , wherein the polyhedral oligomeric silsesquioxane filler is of the general formula R 7 T 4 D 3 (OH) 3 wherein R is a hydrocarbon, n is 6, 8, 10, 12 or higher, m is 1 to n, T is SiO 1.5 , and D is SiO 2 .

14. The polymerizable dental restorative composition of claim 13 , wherein n is 8.

15. The polymerizable dental restorative composition of claim 14 , wherein each R is a phenyl.

16. The polymerizable dental restorative composition of claim 1 , wherein the sol-derived filler has a crystalline phase, and is formed from a nanoparticulate silica sol.

17. The polymerizable dental restorative composition of claim 16 , wherein the sol-derived filler is a zirconium silicate.

18. The polymerizable dental restorative composition of claim 1 , wherein the filler composition further comprises about 1 to about 90 weight % of an additional filler, based on the total weight of the filler composition.

19. The dental restorative material of claim 1 , further comprising a curing system.

20. A method of making a dental restoration, comprising

applying to a site to be restored a polymerizable dental restorative composition, comprising

a curing agent;

a resin composition comprising an oligomer comprising units having the structure:

AB  (I)

wherein A is an organic radical comprising 1 to about 6 (meth)acrylate groups and 0 to about 5 hydroxy groups; and B is an organic radical comprising 1 to about 5 epoxide groups, wherein A and B are linked through the reaction of an epoxide and a hydroxyl group; and

a filler composition comprising

a polyhedral oligomeric silsesquioxane filler; and

a sol-derived filler; and

curing the oligomer to form a dental restoration.

21. A method of manufacturing copolymerizable dental resin composition, comprising mixing

a resin composition comprising an oligomer comprising units having the structure:

AB  (I)

wherein A is an organic radical comprising 1 to about 6 (meth)acrylate groups and 0 to about 5 hydroxy groups; and B is an organic radical comprising 1 to about 5 epoxide groups, wherein A and B are linked through the reaction of an epoxide and a hydroxyl group; and a filler composition comprising

a polyhedral oligomeric silsesquioxane filler; and

a sol-derived filler.

22. A method of making a dental restoration, comprising

applying to a site to be restored a polymerizable dental restorative composition, comprising

a curing agent;

a resin composition comprising an oligomer comprising units having the structure:

AB  (I)

wherein A is an organic radical comprising 1 to about 6 (meth)acrylate groups and 0 to about 5 hydroxy groups; and B is an organic radical comprising 1 to about 5 epoxide groups, wherein A and B are linked through the reaction of an epoxide and a hydroxyl group; and

a filler composition comprising

a polyhedral oligomeric silsesquioxane filler; and

a sol-derived filler; and

curing the oligomer to form a dental restoration.