Copper (Photo)redox Catalyst for Radical Photopolymerization in Shadowed Areas and Access to Thick and Filled Samples

The free radical polymerization of low viscosity methacrylate blends upon a LED irradiation at 405 nm under air is carried out using Cu­(I)/iodonium salt/tin­(II) organic derivative as photoinitiating systems. The system exhibits a high reactivity; where tin derivative plays a crucial role. It operates through a catalytic cycle in which Cu­(I) is regenerated and can be used at low concentrations (0.1–0.3 wt %). Remarkable performances are achieved. At first, a final methacrylate conversion of 82% after 40 s in 1.4 mm thick samples is obtained for an irradiance of 35 mW/cm<sup>2</sup> whereas such a conversion is only reached only when using a Cu­(I)/iodonium salt system under a 200 mW/cm<sup>2</sup> light exposure. Second, a 55% conversion is still obtained after 150 s under a very low irradiance (2.5 mW/cm<sup>2</sup>). Third, almost tack-free thick samples (1.4 mm) under air are produced upon sunlight exposure (65% of conversion for the 1.4 mm thick sample after 90 s of irradiation). Fourth, the photocuring of clear samples as thick as 9 cm (and presumably even more) with an impressive homogeneity through the entire polymerizable medium is feasible; the photopolymerization of 8.5 cm thick filled samples is also realized. Fifth and last, a lateral polymerization beyond the irradiated area is demonstrated with unprecedented extensions of 8 mm (tin­(II) = 1.3%) and 28 mm (tin­(II) = 8%), which allows polymerization reactions to occur in shadowed areas. The chemical mechanisms are studied by steady state photolysis and ESR-spin trapping experiments. The subsequent role of the hydroperoxides (ROOH) formed during the polymerization reaction is a key point i.e. for the polymerization in shadowed areas (thick and filled samples), these latent species (ROOH) will be generated from the oxygen inhibition and can diffuse for a full curing of the samples through a ROOH/Cu­(I) redox initiation.