高性能卟啉POF多相催化剂的结构调控及其催化植物油脂环氧化研究

Many advances have been made in the design and synthesis of porous organic frameworks (POF) with good mechanical stability, high surface area, controlled surface functionality in recent years, and their wide applications in field of catalysis. The metalloporphyrin biomimetic catalysts gave higher conversion and selectivity by catalytic oxidation of hydrocarbons. Unfortunately, when used as homogeneous catalysts, they often suffer from quick degradation such as ligand oxidation or m-oxo dimer formation.And some disadvantages which increased the cost of reactions and limited application, such as the difficult recycle of catalysts after reaction. We report here Pyrenees-based porous organic frameworks (POF) catalyst. Based on total preparation and characterization of POF catalysts-based metalloporphyrin, epoxidation of vegetable oil over POF catalysts were investigated. The epoxidation of oil is mainly used in the vegetable oil. It's a green environmental protection type of plasticizer which has excellent performance. The epoxidation of the model over the catalyst was investigated to explain the mechanism of the epoxidation. Effects of the epoxidation conditions, such as time, reaction temperature, catalyst amount, on the conversion, selectivity, epoxided product structure were investigated mainly. Finally, a potential mechanism is also proposed in this research and the epoxided product of vegetable oil with excellent properties would be obtained. Through the project, it will provide new directions for the high-valuable utilization of vegetable oil.

多孔有机骨架(POF)材料由于具有更大的孔体积和丰富的孔道结构，尤其在酸碱，湿气，高温等苛刻条件下优异的结构稳定性，在催化领域已成为新兴的热点。仿生催化剂金属卟啉能在温和条件下高活性、高选择性的催化烯烃环氧化，但易发生氧化降解使活性降低，而且不易分离重复利用，为解决上述问题，本项目通过共价键连接金属卟啉合成POF催化剂，以云南省丰富的可再生非食用植物油脂资源为研究对象，进行催化植物油脂环氧化研究。首先进行刚性骨架卟啉单元前驱体的设计选择，然后探索高质量、大尺寸、结构有序的的金属卟啉POF催化剂的制备规律；建立高效的催化体系，阐明卟啉POF催化剂的构效关系及结构调控，筛选出高活性和高选择性的可循环利用的多相催化剂；确立卟啉POF催化植物油脂环氧化反应的最佳工艺条件，探索其催化植物油脂环氧化机理，建立卟啉POF催化剂活性中心结构与催化性能调控机制。本项目研究对植物油脂的高值化利用具有重要意义。

云南省的植物油脂资源丰富，大力开发植物油基增塑剂的洁净生产工艺，不仅有利于充分利用可再生油料资源，还具有极大的经济价值。本项目以利用四节点的构筑单元5,10,15,20-四(4-苯基)金属卟啉作为反应单元前驱体，采用温和的反应条件，利用Lewis酸催化的Friedel-Crafts烷基化反应制备含有不同金属中心(Mn、Fe、Co)的金属卟啉POF催化剂。用X-射线粉末衍射(XRD)，傅里叶红外光谱仪（FT-IR）、热重分析仪(TG)、透射电镜(TEM)等测试对合成催化剂进行表征。并对其进行活性评价，在POF催化剂表征的基础上，探讨催化剂POF催化模型物环氧化反应时的性能的调控机制。在对橡胶籽油进行分析表征的基础上，采用POF-1-Mn催化制备环氧橡胶籽油，结果表明，以橡胶籽油为原料，采用POF-1材料催化制备环氧橡胶籽油，确定了制备环氧橡胶籽油的最佳工艺条件，环氧橡胶籽油的性能平均值分别为：环氧值7.27 mol·100g-1，环氧选择性为88.6%，双键转化率为86.5%。通过红外分析、核磁氢谱和碳谱进一步证实了环氧基团的生成。本项目为植物油脂的开发利用提供了有益的探索。