UV intensity, temperature and dark-curing effects in cationic photo-polymerization of a cycloaliphatic epoxy resin

A difunctional cycloaliphatic epoxy monomer was cationically photo-polymerized in the presence of a diaryliodonium salt photoinitiator and an isopropyl thioxanthone photosensitizer at different temperatures and UV intensities. The photo-polymerization kinetics and structure formation were analysed using photo-DSC, IR spectroscopy and photo-rheology. An autocatalytic relation was used to model the conversion state with Arrhenius and power-law relationships for temperature and light intensity dependence. Conversion was found to depend on sample thickness, following the Beer-Lambert law. Photo-rheology measurements showed that the system vitrified before gelation at ambient temperature, and after gelation at high temperature under intense UV illumination. Time temperature transformation and time intensity transformation diagrams were built. Moreover, isothermal dark-curing enabled significant conversion increases up to the occurrence of vitrification, while thermal post-curing above Tg led to conversion as high as 71%. Thermo-mechanical measurements enabled to quantify Tg and the effects of the increase in conversion provided by thermal post-curing.