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

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.

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.

A method of generating a polymeric material, the method comprising polymerizing at least partially 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;

• (b) an ene monomer, and optionally a polymerization photoinitiator.