Abstract
New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in this study based on H-1 and (1)3C NMR and FTIR spectroscopic analyses through the reduction of Schiff base formed from tetrakis(4-aminophenyl)porphyrin (TAPP) and salicylaldehyde and the subsequent reaction with CH2O. Thermal properties of the product formed through ring-opening polymerization (ROP) of Por-BZ were measured using DSC, TGA and FTIR spectroscopy. Because of the rigid structure of the porphyrin moiety appended to the benzoxazine unit, the temperature required for ROP (314 degrees C) was higher than the typical Pa-type benzoxazine monomer (ca. 260 degrees C); furthermore, poly(Por-BZ) possessed a high thermal decomposition temperature (T-d10 = 478 degrees C) and char yield (66 wt%) after thermal polymerization at 240 degrees C. An investigation of the thermal and luminescence properties of metal-porphyrin complexes revealed that the insertion of Ni and Zn ions decreased the thermal ROP temperatures of the Por-BZ/Ni and Por-BZ/Zn complexes significantly, to 241 and 231 degrees C, respectively. The metal ions acted as the effective promoter and catalyst for the thermal polymerization of the Por-BZ monomer, and also improved the thermal stabilities after thermal polymerization.