Dental composites systems and methods of making the same and using same

Patent metadata

Field	Value
Publication number	US-9700492-B2
Application number	US-201514640809-A
Country	US
Kind code	B2
Filing date	Mar 6, 2015
Priority date	Mar 7, 2014
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

The invention includes a composition comprising a vinyl sulfone monomer, a thiol monomer, and optionally an isocyanate monomer. The invention further includes a composition comprising a composition comprising the tetra(2-mercapto)silane (SiTSH) monomer and at least one selected from the group consisting of (a) a Michael acceptor, optionally an isocyanate monomer, and optionally at least one catalyst selected from the group consisting of a base, nucleophile, photolabile base, photolabile nucleophile, and mixtures thereof; (b) an ene monomer, and optionally a polymerization photoinitiator. In certain embodiments, once the composition is polymerized, the polymerized system is suitable for use as a dental composite system. In other embodiments, the polymerized system is stable to acidic and basic conditions. In yet other embodiments, the polymerized system forms microparticles. The invention further includes a method of generating a dental polymeric material.

First claim

What is claimed:

1. A composition comprising one or more multifunctional vinyl sulfone monomers, one or more multifunctional thiol monomers, and at least one isocyanate monomer,
wherein (i) at least one multifunctional thiol monomer is trifunctional, tetrafunctional, pentafunctional or hexafunctional as to the thiol group, or (ii) at least one vinyl sulfone monomer is trifunctional, tetrafunctional, pentafunctional or hexafunctional as to the vinyl sulfone group;
wherein the one or more multifunctional vinyl sulfone monomers, the one or more multifunctional thiol monomers and the at least one isocyanate monomer are devoid of ester functionalities;
wherein the at least one isocyanate monomer is selected from the group consisting of a monofunctional isocyanate, a polyfunctional isocyanate, and mixtures thereof;
wherein (i) the thiol equivalent concentration is approximately equal to the sum of the vinyl sulfone equivalent and the isocyanate equivalent concentrations, or (ii) the thiol equivalent, vinyl sulfone equivalent and isocyanate equivalent concentrations are selected such that, upon polymerization of the composition, at least 80% polymerization of the thiol monomer or vinyl sulfone monomer is observed; and
wherein, once polymerized, the polymerized composition comprises a crosslinked polymeric network.

2. The composition of claim 1 , wherein the monomers in the composition are unpolymerized or at least partially polymerized.

3. The composition of claim 1 , further comprising at least one catalyst selected from the group consisting of a base, a nucleophile, a photolabile base, a photolabile nucleophile, and mixtures thereof.

4. The composition of claim 3 , wherein the composition undergoes at least partial polymerization when the catalyst is photocleaved.

5. A composition comprising one or more multifunctional vinyl sulfone monomers, one or more multifunctional thiol monomers, and optionally an isocyanate monomer,
wherein the one or more multifunctional vinyl sulfone monomers, the one or more multifunctional thiol monomers and the optional isocyanate monomer are devoid of ester functionalities;
wherein, once polymerized, the polymerized composition comprises a crosslinked polymeric network;
wherein at least one vinyl sulfone monomer is selected from the group consisting of divinyl sulfone,

and any combinations thereof; and,
wherein at least one thiol monomer is selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane, 2,3-dimercapto-1-propanol, 2-mercapto-ethyl sulfide, 2,3-(dimercaptoethylthio)-1-mercaptopropane, 1,2,3-trimercaptopropane, 1,6-hexanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, isophorone diurethane thiol,

and any combinations thereof.

6. The composition of claim 1 , wherein the one or more thiol monomers are independently difunctional, trifunctional, tetrafunctional, pentafunctional or hexafunctional as to the thiol group, and wherein the one or more vinyl sulfone monomers are independently difunctional, trifunctional, tetrafunctional, pentafunctional or hexafunctional as to the vinyl sulfone group.

7. A method of photoinducing a thiol-Michael addition reaction, the method comprising photo-irradiating a composition comprising a thiol monomer, a Michael acceptor monomer, at least one isocyanate monomer, and at least one catalyst selected from the group consisting of a photolabile base, a photolabile nucleophile, and mixtures thereof;
wherein the at least one isocyanate monomer is selected from the group consisting of a monofunctional isocyanate, a polyfunctional isocyanate, and mixtures thereof; and
wherein (i) the thiol equivalent concentration is approximately equal to the sum of the vinyl sulfone equivalent and the isocyanate equivalent concentrations, or (ii) the thiol equivalent vinyl sulfone equivalent and isocyanate equivalent concentrations are selected such that upon polymerization of the composition, at least 80% polymerization of the thiol monomer or vinyl sulfone monomer is observed.

8. The method of claim 7 , wherein the photolabile base or photolabile nucleophile comprises a protective group selected from the group consisting of:

wherein:
each occurrence of R 1 and R 2 is independently H or OCH 3 ,
each occurrence of R 3 is independently H, CH 3 , C(═O)OH or C(═O)OCH 3 ,
X is NH or O, and
each occurrence of R 4 and R 5 is independently H or CH 3 .

9. The method of claim 7 , wherein the at least one catalyst comprises a tertiary amine, wherein each substituent on the tertiary amine or phosphine is independently selected from the group consisting of alkyl, substituted alkyl, aryl and substituted aryl.

10. The method of claim 7 , wherein the Michael acceptor monomer comprises a (meth)acrylate, maleamide, or vinyl sulfone.

11. The method of claim 7 , wherein photo-irradiating the composition promotes at least partial polymerization of the monomers.

12. The method of claim 7 , wherein the composition further comprises a filler comprising a thiol- or a vinyl sulfone-functionalized particle.

13. A composition comprising a multifunctional vinyl sulfone monomer, a tetra(2-mercapto)silane (SiTSH) monomer, and optionally an isocyanate monomer, wherein, once polymerized, the polymerized composition forms a crosslinked polymeric network.

14. The composition of claim 13 , wherein the monomers in the composition are unpolymerized or at least partially polymerized.

15. The composition of claim 13 , wherein the isocyanate monomer is absent; and wherein (i) the thiol equivalent concentration is approximately equal to the vinyl sulfone equivalent concentration, or (ii) the thiol equivalent and vinyl sulfone equivalent concentrations are selected such that, upon polymerization of the composition, at least 80% polymerization of the thiol or vinyl sulfone monomers is observed.

16. The composition of claim 13 , wherein the isocyanate is present and is selected from the group consisting of a monofunctional isocyanate, a polyfunctional isocyanate, and mixtures thereof.

17. The composition of claim 16 , wherein (i) the thiol equivalent concentration is approximately equal to the sum of the vinyl sulfone equivalent and the isocyanate equivalent concentrations, or (ii) the thiol equivalent, vinyl sulfone equivalent and isocyanate equivalent concentrations are selected such that, upon polymerization of the composition, at least 80% polymerization of the thiol monomer or vinyl sulfone monomer is observed.

18. The composition of claim 13 , wherein the composition is essentially free of any other thiol monomer apart from SiTSH.

19. The composition of claim 13 , wherein the at least partially polymerized composition is stable to acidic or basic conditions.

20. The composition of claim 13 , wherein the monomers are at least partially polymerized by step-growth dispersion click chemistry to form microspheres.

21. The composition of claim 20 , wherein the microspheres have an average diameter within a range selected from the group consisting of: from 0.5 μm to 100 μm, from 1 μm to 50 μm, from 0.5 μm to 1 μm; and from 1 μm to 10 μm.

22. The composition of claim 20 , wherein the microspheres are near-monodisperse or monod

Assignees

• Univ Colorado Regents

Inventors

• Bowman Christopher N
• Xi Weixian
• Chatani Shunsuke
• Gong Tao
• Nair Devatha P
• Podgorski Maciej

Classifications

• A61K6/891 Primary

  Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• C08G18/3876 Primary

  containing mercapto groups · CPC title

• A61K6/73

  comprising sulfur-containing compounds · CPC title

• C08G18/677

  containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups · CPC title

• C08G18/73

  acyclic · CPC title