Abstract:

Dehydroabietic phenylphosphine diester(DPD), a novel rosin-based derivative, was synthesized by one-step synthesis. The new self-assembled nanoscale rosin-hydroxyapatite(HAP) hybrid materials were successfully prepared via in-situ sol-gel method under mild conditions using the synthesized DPD as organic phosphorus source. The effects of Ca/P molar ratio, pH value and temperature on the morphology and size of hybrid materials were investigated. Moreover, the hydrolysis of organic molecules and the formation process of complexes were proposed based on quantum chemistry calculation. The results showed that the peaks of 1 730, 1 800 cm^-1 and δ 185.33 in the FT-IR and the ¹³C NMR spectrum demonstrated the synthesis of phosphoesters. The peaks at 22.9°, 21.8°, 16.8°, 45.3°, and 25.9° in the XRD spectrum belonged to the crystalline structure of hydroxyapatite. The mass fraction of organic compounds in the rosin-HAP hybrid materials could reach more than 40%. Quantum chemistry calculation showed that the relatively stable rosin phosphate calcium complexes were formed.When the molar ratio of calcium to phosphorus was 1∶10, the mass fraction of pure organic compounds and complexes were close to 70% and 20%, respectively. The morphology and size of hybrid materials could be well controlled by the presence of the DPD. As the molar ratio of calcium to phosphorus decreased, the particle size of the hybrid material tended to decrease. At the same time, the hybrid materials were stacked in sheet shape under acidic conditions, while they were stacked in rod shape under alkaline conditions. The ability of hybrid materials to adsorb phenol was also studied. It was found that the amount of phenol adsorption increased with the increase of the proportion of dehydrobialate benzene rings in the hybrid materials, and the maximum amount reached 32 mg/g. It showed that hybrid materials had good application prospects for the treatment of sewage containing aromatic compounds such as phenol.

Key words: rosin-HAP hybrid materials, sol-gel method, low temperature, in-situ reaction