We have prepared semi-interpenetrating polyacrylate networks (PA/BA-m s-IPNs) through rapid photo-polymerization of a triacrylate monomer (TMPTA) in the presence of a photomitiator (1184), a tetramercaptane transfer agent (4SH), and N-methyl-bisbenzoxazine (BA-m). Next, we prepared novel fully interpenetrating polyacrylate (PA) and polybenzoxazine (PBZ) networks (PA/PBZ f-IPNs) through thermal polymerization of the BA-m monomer at 180 degrees C for 4 h. For the PA/BA-m s-IPNs, the BA-m monomers can be frozen and dispersed in the UV-cured PA network within 5 min to inhibit macrophase separation. After thermal polymerization, the phenol units of the ring-opened PBZ segments can form a hydrogen-bonding interface with the carbonyl groups to improve the compatibility between the PBZ microdomains and the PA networks. From an analysis using Kissinger's method, the non-isothermal kinetics of the thermal polymerization for the PA/BA-m s-IPNs indicate that an increase in the PA content increased the steric hindrance of PBZ polymerization. We used DSC, TGA, and contact angle analyses to determine the glass transition temperature, thermal stability, and surface free energy, respectively, of the PA/PBZ f-IPNs. The thermal stability and surface free energy of these PA/PBZ f-IPNs display linear relationships with respect to the PBZ content. Crown Copyright (C) 2008 Published by Elsevier Ltd. All rights reserved.