The cationic ring-opening polymerization (CROP) of 2-oxazolines gives polymers with unique characteristics arising from its polyamide backbones and structural versatility. Up to now, poly(2-oxazoline)s were obtained by classical thermal polymerization methods not aiming for application in bulk curing of structural polymers. We introduce the cationic photopolymerization of 2-oxazolines at elevated temperatures for the direct UV-induced curing of materials with exclusive chemical and structural particularities. After efficient photoinitiation via onium salt photoacid generators (PAGs), the immanent low-rate propagation is crucially promoted by thermal energy input to the ring-opening reaction. In simultaneous thermal analysis (STA), photo-DSC, and (thermo)mechanical analyses we investigated the UV-induced CROP of 2-oxazolines in a temperature range of 100-140 °C and show the exceptional potential of the introduced photopolymers. Furthermore, we applied the photopolymerizable system in Hot Lithography, a stereolithography-based 3D printing technology at elevated temperatures.
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