Photopolymerization is a widely used technique to synthesize polymers and hydrogels. The commonly used ultraviolet (UV)-curable mono-, di- or multifunctional vinylated monomers are often volatile, causing difficulty in kinetics analysis such as photo-differential scanning calorimetry (PhotoDSC). In this work, the DSC sample pan is chemically and physically modified such that the resin can be placed uniformly in the sample pan with minimum sample weight loss during measurement. This approach substantially improved experimental accuracy, which in turn provides a better understanding of the reaction kinetics of UV-curable polymers. Kinetic experiments were carried out for poly(2-hydroxyethyl methacrylate) (HEMA)-based hydrogels. The effects of light intensity and water concentration on the reaction kinetics and rheological change was investigated. It was found that increasing the light intensity enhances the polymerization, but too high an intensity slows down the reaction at the later stage. The addition of solvent and high light intensity facilitates the cyclization, delaying macrogelation. The viscosity rise of the resin system and the formed polymer size were also measured using a photorheometer and a particle size analyzer, respectively. The measured gel time, gel conversion and polymer size distribution agree with the kinetic analysis. (c) 2005 Elsevier Ltd. All rights reserved.