Dental resin composition, method of manufacture, and method of use thereof

1. A curable (meth)acrylate resin for dental compositions, comprising:

a compound according to Structure IIIa

wherein

M is selected from the group consisting of phenyl, C 1 -C 3 alkylphenyl, and C 5 -C 14 alkylene;

G is an aromatic hydrocarbyl group;

X 1 is O or —NR 1 ;

Q is substituted or unsubstituted C 1 -C 16 alkylene, arylene, —C 1 -C 4 alkyl-aryl-C 1 -C 4 alkyl-, or polyether, wherein when Q is substituted, the substituents are selected from the group consisting of cyano, hydroxyl, nitro, azido, alkanoyl, carboxamido, alkyl, alkoxy, aryloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, aminoalkyl, aryl, alkylaryl, arylalkoxy, aromatic heterocyclic, and combinations thereof;

R 1 is hydrogen, a substituted or unsubstituted alkyl, alkenyl, aryl, or -alkylaryl group, wherein when R 1 is substituted, substituents are selected from the group consisting of alkyl, aryl, alkylaryl, arylalkoxy, and aromatic heterocyclic;

R 2 is H or methyl;

each instance of R 3 is independently hydrogen or C 1 -C 12 alkyl;

x is 1 or 2;

q is 0 or 1;

n 1 is 2; and

n 2 is 1 or 2;

wherein the curable (meth)acrylate resin is free of units derived from bisphenol A or bisphenol A analogs; and

wherein the curable (meth)acrylate resin is a reaction product obtained by

i) reacting an anhydride with an alcohol M(OH) p or an amine M(NR 1 H) p , wherein p=1, 2, 3, 4, 5 or 6 to obtain a carboxy ester or a carboxy amide, and

ii) reacting the carboxy ester or carboxy amide with a (meth)acrylate monomer comprising an epoxide group or an oxetane group to obtain a curable (meth)acrylate resin for dental compositions.

2. The curable (meth)acrylate resin of claim 1 , comprising:

a compound according to Structure IIIb

wherein

G is phenyl;

R 4 and R 5 are each independently hydrogen, or C 1 -C 12 alkyl; and

y is 1, 2, 3, 4, 5, 6, 7, or 8.

3. The curable (meth)acrylate resin of claim 1 , comprising a compound according to Structure IV

4. The curable (meth)acrylate resin of claim 1 , wherein the G group is derived from trimellitic anhydride, pyromellitic dianhydride, 3,3′,4,4′ benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, or a combination of the foregoing anhydrides.

5. The curable (meth)acrylate resin of claim 1 , wherein G is phenyl.

6. The curable (meth)acrylate resin of claim 1 , wherein Q is C 1 -C 3 alkylene.

7. The curable (meth)acrylate resin of claim 1 , wherein X 1 is O.

8. A dental resin composition that exhibits low shrinkage upon cure comprising the curable resin of claim 1 , a co-polymerizable ethylenically unsaturated oligomer, a polymerization initiator for speeding the cure, an optional polymerization accelerator, an optional filler, and an optional diluent monomer, wherein the curable resin is present in an amount of about 50 to about 99 weight percent based on the total weight of polymerizable components.

9. The dental resin composition of claim 8 , wherein the polymerizable ethylenically unsaturated monomer or oligomer is free of units derived from bisphenol A or bisphenol A analogs.

10. The dental resin composition of claim 8 , having a shrinkage after cure of less than 4 volume percent as measured by mercury dilatometer.

11. The dental resin composition of claim 8 , comprising filler and having a shrinkage after cure of less than 2 volume percent.

12. A method of making a dental restoration, comprising:

mixing a curable resin, a co-polymerizable ethylenically unsaturated monomer or oligomer, a polymerization initiator, an optional polymerization accelerator, an optional filler, and an optional diluent monomer to form a dental composition;

applying the dental composition to a tooth to be repaired; and

curing the dental composition, wherein the curable resin is a compound according to Structure IIIa

wherein

M is selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, aryl, -alkylaryl, a polyester, a polyether, a polyurethane, a polycaprolactone group, and combinations thereof, wherein when M is substituted, substituents are selected from the group consisting of cyano, nitro, azido, alkanoyl, carboxamido, alkyl, alkoxy, aryloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, aminoalkyl, aryl, alkylaryl, arylalkoxy, aromatic heterocyclic, and combinations thereof;

G is an aromatic hydrocarbyl group;

X 1 is O or —NR 1 ;

Q is substituted or unsubstituted C 1 -C 16 alkylene, arylene, —C 1 -C 4 alkyl-aryl-C 1 -C 4 alkyl-, or polyether, wherein when Q is substituted, the substituents are selected from the group consisting of cyano, hydroxyl, nitro, azido, alkanoyl, carboxamido, alkyl, alkoxy, aryloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, aminoalkyl, aryl, alkylaryl, arylalkoxy, aromatic heterocyclic, and combinations thereof;

R 1 is hydrogen, a substituted or unsubstituted alkyl, alkenyl, aryl, or -alkylaryl group, wherein when R 1 is substituted, substituents are selected from the group consisting of alkyl, aryl, alkylaryl, arylalkoxy, and aromatic heterocyclic;

R 2 is H or methyl;

each instance of R 3 is independently hydrogen or C 1 -C 12 alkyl;

x is 1 or 2;

q is 0 or 1;

n 1 is 2; and

n 2 is 1 or 2;

wherein the curable (meth)acrylate resin is free of units derived from bisphenol A or bisphenol A analogs; and

wherein the curable (meth)acrylate resin is a reaction product obtained by

i) reacting an anhydride with an alcohol M(OH) p or an amine M(NR 1 H) p , wherein p=1, 2, 3, 4, 5 or 6 to obtain a carboxy ester or a carboxy amide, and

ii) reacting the carboxy ester or carboxy amide with a (meth)acrylate monomer comprising an epoxide group or an oxetane group to obtain a curable (meth)acrylate resin for dental compositions.

13. The method of claim 12 , wherein the M group is derived from methanol, ethanol, 1-butanol, 2-propanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-1-butanol, benzyl alcohol, 1-phenethyl alcohol, 2-phenethyl alcohol, 2-phenyl-1-propanol, phenol, polyester polyol, polycarbonate polyol, polyurethane polyol, polycaprolactone polyol, methylamine, 1-aminoethane, 1-aminobutane, or 1,6-hexanediamine.

14. The method of claim 12 , wherein M is phenyl, C 1 -C 3 alkylphenyl, or C 5 -C 14 alkylene.

15. A method of making a curable (meth)acrylate resin for dental compositions, comprising:

i) reacting an anhydride with an alcohol M(OH) p or an amine M(NR 1 H) p , wherein p=1, 2, 3, 4, 5, or 6, M is phenyl, C 1 -C 3 alkylphenyl, and C 5 -C 14 alkylene, and R 1 is hydrogen, a substituted or unsubstituted alkyl, alkenyl, aryl, or -alkylaryl group to obtain a carboxy ester or a carboxy amide; and

ii) reacting the carboxy ester or carboxy amide with a (meth)acrylate monomer comprising an epoxide group or an oxetane group to obtain a curable (meth)acrylate resin according to Structure IIIa

wherein

M is selected from the group consisting of phenyl, C 1 -C 3 alkylphenyl, and C 5 -C 14 alkylene;

G is an aromatic hydrocarbyl group;

X 1 is O or —NR 1 ;

Q is substituted or unsubstituted C 1 -C 16 alkylene, arylene, —C 1 -C 4 alkyl-aryl-C 1 -C 4 alkyl-, or polyether, wherein when Q is substituted, the substituents are selected from the group consisting of cyano, hydroxyl, nitro, azido, alkanoyl, carboxamido, alkyl, alkoxy, aryloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, aminoalkyl, aryl, alkylaryl, arylalkoxy, aromatic heterocyclic, and combinations thereof;

R 1 is hydrogen, a substituted or unsubstituted alkyl, alkenyl, aryl, or -alkylaryl group, wherein when R 1 is substituted, substituents are selected from the group consisting of alkyl, aryl, alkylaryl, arylalkoxy, aromatic heterocyclic, and combinations thereof;

R 2 is H or methyl;

each instance of R 3 is independently hydrogen or C 1 -C 12 alkyl;

x is 1 or 2;

q is 0 or 1;

n 1 is 2; and

n 2 is 1 or 2;

wherein the curable (meth)acrylate resin is free of units derived from bisphenol A or bisphenol A analogs.

16. The method of claim 15 , wherein the anhydride is trimellitic anhydride, pyromellitic dianhydride, 3,3′,4,4′ benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, or a combination of the foregoing anhydrides.

17. The method of claim 15 , wherein the alcohol is methanol, ethanol, 1-butanol, 2-propanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-1-butanol, benzyl alcohol, 1-phenethyl alcohol, 2-phenethyl alcohol, 2-phenyl-1-propanol, or phenol; and wherein the amine is methylamine, 1-aminoethane, 1-aminobutane, or 1,6-hexanediamine.

18. The method of claim 15 , wherein the (meth)acrylate monomer comprising an epoxide group or an oxetane group comprises a structure

wherein Z is an epoxide or an oxetane group.

19. A curable (meth)acrylate resin for dental compositions, comprising:

a compound according to Structure IV:

20. A dental resin composition comprising the curable resin of claim 19 , a co-polymerizable ethylenically unsaturated oligomer, a polymerization initiator, an optional polymerization accelerator, an optional filler, and an optional diluent monomer, wherein the curable resin is present in an amount of about 50 to about 99 weight percent based on the total weight of polymerizable components.