In this study, 2-hydroxyethyl acrylate (HEA) was polymerized to obtain polymers that can be used as hydrogel and copolymerized for biomedical applications. Bulk, solution, and atom transfer radical polymerization (ATRP) techniques at different temperatures were applied. The polymerization in bulk form was carried out in vacuum and in open atmosphere. The polymerization curves showed autoacceleration mechanism and the limiting conversion was 100%. The polymers obtained were insoluable in most common solvents because of high molecular weights and strong intermolecular hydrogen bonding. They absorb more than 30% (w/w) water as hydrogel. To decrease the molecular weight and obtain soluble polymers, HEA was polymerized in solution by ATRP method, which also gave insoluble hydrogel type polymers. The activation energy for bulk polymerization was 155.8 kJ/mol, which is very high for a free radical polymerization. This is due to the high degree of intermolecular hydrogen bonding, which was also supported by FTIR and TGA analysis. The polymers were characterized by FT-IR, DSC, TGA, and H-1 NMR techniques. (c) 2005 Wiley Periodicals, Inc.