Evaluation of a photo-initiated copper(I)-catalyzed azide-alkyne cycloaddition polymer network with improved water stability and high mechanical performance as an ester-free dental restorative.

Objective: The objective is to develop and characterize an ester-free ether-based photo-CuAAC resin with high mechanical performance, low polymerization-induced stress compared with common BisGMA/TEGDMA (70/30) resins, and improved water stability in comparison to previously developed urethane-based photo-CuAAC resins.

Methods: Triphenyl-ethane-centered ether-linked tri-azide monomers were synthesized and co-photopolymerized with ether-linked tri-alkyne monomers under visible light irradiation using a copper(II) pre-catalyst and CQ/EDAB as the initiator. The ether-based CuAAC formulation was investigated for thermo-mechanical properties, polymerization kinetics and shrinkage stress, and flexural properties with respect to a conventional BisGMA/TEGDMA (70/30) dental resin.

Stress Relaxation via Covalent Dynamic Bonds in Nanogel-Containing Thiol-Ene Resins.

Functional nanogels are attractive additives for use in polymer composites. In this study, nanogels with internal allyl sulfide moieties throughout their network structure were prepared via a thiol-Michael addition reaction. The excess thiol-functionalized nanogels were less than 60 nm as discrete particles but act as room-temperature liquids in the bulk state.

Step-growth Production of Nanogels for Use as Macromers with Dimethacrylate Monomers.

A series of functional nanogels were synthesized by a step-growth mechanism that involved diisocyanate addition to a modest stoichiometric excess of multi-thiols. Nanogels with sizes less than 10 nm were obtained as room temperature liquids with residual thiol groups used to attach methacrylate functionality. Depending on nanogel structure, bulk nanogel properties varied widely, as did the properties of the nanogel-derived and nanogel-modified polymers.

-Nitrobenzyl-Based Photobase Generators: Efficient Photoinitiators for Visible-Light Induced Thiol-Michael Addition Photopolymerization.

In this contribution, three -nitrobenzyl-based photobase systems were synthesized and evaluated for visible light initiated thiol-Michael addition polymerizations. With a modified structure, the (3,4-methylenedioxy-6-nitrophenyl)-propyloxycarbonyl (MNPPOC) protected base performance exceeds that of the nonsubstituted 2-(2-nitrophenyl)-propyloxycarbonyl (NPPOC) protected base and an ITX sensitized photobase system, with respect to both long-wavelength light sensitivity and photolytic efficiency. In material synthesis, MNPPOC-TMG is capable of initiating photo thiol-Michael polymerization efficiently and orthogonally with only limited visible light exposure and generating a highly homogeneous cross-linked polymer network.