Photopolymerization offers substantial advantages in terms of time, temperature, energy consumption, and spatial control of the initiation. The application however is strongly limited due to the constrained penetration of light into thick films. Strategies to overcome the problem of limited curing depth, as well as to improve the curing of shadow areas, involve dual curing, frontal polymerization, and upconversion of particles. Whereas excellent results have been accomplished applying photofrontal polymerization on a theoretical level, few studies report on practical applications achieving high curing depth within short time. This study aims to investigate the potential of photofrontal polymerization, performed only with photoinitiator and light, for the fast and easy production of several-centimeter-thick (meth)acrylic layers. Monomer/ initiator systems were evaluated with respect to their optical density as well as photobleaching behavior. Moreover, depth-dependent polymerization was studied in specimens of varying monomer ratio and photoinitiator concentration. When an ideal photoinitiator concentration was selected, curing up to 52 mm in depth was accomplished within minutes.

Photopolymerization has undergone significant development in recent years. It enables fast and easy processing of materials with customized properties and allows precise printing of complex surface geometries. Nevertheless, photopolymerization is mainly applied to cure thin films since the low curing depth limits the fast production of large volumes. Frontal photopolymerization (FPP) is suitable to overcome these limitations so that curing of centimeter-thick (meth)acrylic layers can be accomplished within minutes by light induction only. Prerequisites, however, are the low optical density of the resin and bleaching ability of the photoinitiator. To date, tailored FPP-resins are not commercially available. This study discusses the potential of long-chain polyether dimethacrylates, offering high-temperature resistance and low optical density, as crosslinkers in photobleaching resins and investigates the mechanical properties of photofrontally-cured copolymers. Characteristics ranging from ductile to hard and brittle are observed in tensile tests, demonstrating that deep curing and versatile material properties are achieved with FPP. Analyzed components display uniform polymerization over a depth of four centimeters in Fourier transform infrared spectroscopy and swelling tests.