New hydrogen donors for amine-free photoinitiating systems in dental materials

Abstract

Objectives: The two-component Camphorquinone (CQ)/aromatic amine system is well-established and clearly corresponds to the reference system used in all photopolymerizable dental adhesives and composites. However, this CQ/amine system still suffers from the presence of aromatic amines that can be referenced as toxic. Therefore, the aim of this work is to develop amine-free photoinitiating systems (PISs) for the polymerization of a representative dental methacrylate resins upon blue light irradiation. The proposed strategy is based on the in-silico design (by molecular modelling) of new hydrogen donors (amine-free) bearing a copolymerizable moiety (methacrylate functionality) to ensure their low migration/leaching properties from the synthesized polymer. The new proposed PISs are compared to the well-established CQ/amine system for the polymerization of different methacrylate blends upon exposure to a commercial blue dental LED centered at 477 nm.

Methods: Molecular orbitals calculations are used to design new hydrogen donors exhibiting low C-H bond dissociation energies. Based on this in-silico design, the syntheses of new co-initiators are reported here for the first time. Real-time FTIR experiments are used to monitor the photopolymerization profiles. Color indexes measurements were also carried out to investigate the bleaching properties of the new proposed systems.

Results: Three new co-initiators are proposed as alternatives to aromatic amines in dental materials in combination with camphorquinone. The performances of the new proposed amine-free PISs for the photopolymerization of thick (1.4 mm) samples of methacrylate upon exposure to a blue dental LED under air are excellent. Similar or better polymerization performances are obtained with the new proposed amine-free systems compared to those reached with the CQ/amine reference. Excellent bleaching properties are also found. The involved chemical mechanisms are investigated through molecular orbitals calculations.

Keywords: Amine-Free systems; Camphorquinone; Co-Initiators; Photoinitiator.