In this report, we designed a new and simple salicylaldehyde azine-functionalized benzoxazine (Azine-BZ) monomer via Mannich condensation reaction of aniline and paraformaldehyde with 1,2-bis(2,4-dihydroxybenzylidene)hydrazine in 1,4-dioxane. Compared with 10 3-phenyl-3,4-dihydro-2H-benzooxazine monomer (263 °C), the maximum exothermic peak of Azine-BZ was shifted to a lower temperature (213 °C) based on differential scanning calorimetry (DSC) analyses because of the basicity of the phenolic group (OH) in the ortho position and the azine groups. Blending Azine-BZ with different weight ratios of zinc perchlorate [Zn(ClO 4 ) 2 ] to form benzoxazine/zinc ion complexes not only afflicted the thermal properties based on thermogravimetric analysis (TGA) due to physical crosslinking through metal-ligand interactions, but also expedite ring-opening polymerization, decreasing the curing temperature from 15 213 to 184 °C (at 10 wt% Zn 2+ ). Based on the fluorescence results, the Azine-BZ and AZine-BZ/Zn(ClO 4 ) 2 complexes were nonemissive in THF solution. Their fluorescence increased gradually upon on the addition of water contents as poor solvent. Interestingly, both the pure Azine-BZ and blending wotj Zn(ClO 4 ) 2 still emitted light after thermal curing at 150 °C, as determined through photoluminescence measurements, indicating that the azine group could act as a probe of the curing behavior of the benzoxazine monomer, as well as a fluorescent chemosensor for Zn 2+ and, possibly, other transition metal ions through a metal-ligand charge transfer 20 mechanism. 45 polybenozoxazine chemistry offers flexibility of many molecular designs, thereby facilitating the preparation of different PBZ nanocomposites. To control the properties of PBZs, several derivatives functionalized with reactive groups A new salicylaldehyde azine-functionalized benzoxazine (Azine-BZ) monomer formed benzoxazine/zinc ion complexes 5 that not only improved the thermal properties but also facilitated ring-opening polymerization.

Hierarchical lamellae-within-lamellae structure for the PTyr/AzoPy-C16 supramolecular complex, featuring long-range-ordered lamellae arising from the PTyr within lamellae arising from AzoPy-C16 units oriented in a perpendicular manner.