新型松香衍生物的一步法合成及杂化材料的温和条件制备

One Step Synthesis of Novel Natural Rosin Derivative and Green Synthesis of Its Hybrid Materials at Mild Temperature

采用一步合成法合成了新型松香基衍生物脱氢枞基苯基膦二酯(DPD),并在温和条件下,以新合成的DPD为有机磷源,采用原位反应,通过溶胶-凝胶法制备了新型自组装纳米级松香-羟基磷灰石(HAP)杂化材料。研究了钙磷物质的量比、pH值和温度对杂化材料形貌和尺寸的影响。此外,基于量子化学计算提出了有机分子的水解和配合物的形成过程。结果表明,FT-IR和^(13)C NMR谱中1730、1800 cm^(-1)和δ185.33处的峰均证明磷酯的合成,而XRD谱图中的22.9°、21.8°、16.8°、45.3°和25.9°处的峰表明羟基磷灰石结晶结构的存在。松香-羟基磷灰石杂化材料中有机物的质量分数可达40%以上,量子化学计算表明形成了较稳定的松香磷酯-钙配合物。当钙磷的物质的量比为1∶10时,纯有机化合物和配合物的质量分数分别接近70%和20%。DPD的存在可以很好地控制杂化材料的形态和尺寸,随着钙磷的物质的量比减小,杂化材料粒径呈减小趋势。同时,酸性条件下杂化材料呈片状堆积,而碱性条件下呈棒状堆积。研究了杂化材料吸附苯酚的能力,发现杂化材料中脱氢枞酸苯环比例的增加,可大幅提高苯酚吸附量,最大吸附量达到32 mg/g,表明杂化材料对处理含苯酚等芳香族化合物的污水具有较好应用前景。

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 1730,1800 cm^(-1)andδ185.33 in the FT-IR and the ^(13)C 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.