新型介孔固体酸催化烯基芳香化合物高效清洁合成研究

Alkenylation of arenes with alkynes has been considered as a novel simple, clean and atom-economic approach for synthesizing alkenylaromatic compounds, one of the most important fine chemicals. The alkenylation catalysts are mainly focused on precious metals or organometallic compounds. Due to their high cost and difficult separation, to replace them with acid catalysts is a promising approach. The use of microporous zeolite overcomes the inherent shortcomings of liquid acids, but the low catalytic efficiency, poor selectivity and heavy alkyne-polymerization remain to be resolved. Therefore, this proposed work is, based on the difference in reactivity and molecular size of to fabricate novel and highly-efficient mesoporous solid acid catalysts, and to adjust and control the diffusion of reactants and alkenylated products, activation of alkynes and collision process of arenes with the produced alkenyl cations through tuning the acidic properties, pore-structure and morphology of novel mesoporous solid acids. The purpose is to resolve the open problems in existing solid acid in alkenylation reactions. Various characterization techniques would be employed to reveal the relationship between the catalyst nature and catalytic performance of the fabricated novel mesoporous solid acids. Moreover, the assistance effect of microwave on the mesoporous solid acid catalysts on the alkenylation reactions would also be investigated. The intensification effect of microwave on the catalytic properties of the fabricated mesoporous solid acids for the alkenylation reactions would be discussed via correlating the catalytic properties and the change of nature for the fresh and spend catalysts under the microwave and conventional heating conditions, and also investigating the temperature rise behavior of mesoporous solid acid catalysts in the microwave field. The main objective of this proposed work is to lay a solid foundation for the highly-efficient and clean synthesis of alkenylaromatic compounds.

芳烃与炔的烯基化是合成烯基芳香化合物这一重要精细化学品的简单、清洁、原子经济的新路线。烯基化催化剂多用贵金属或有机金属，存在价格高、分离难等问题，而酸催化则颇具前景。沸石克服了液体酸所固有的一些缺点，但其仍存在底物适用范围窄、催化效率低、选择性差和炔聚合严重的不足。为此，本项目拟针对不同底物反应性质和分子尺寸的差异，构建新型高效的介孔固体酸，通过酸性质、孔结构和形貌的调节并结合微波强化技术的运用以对反应底物和烯基化产品的扩散、炔的活化及芳烃与烯基阳离子之间的碰撞过程进行调控，从而解决现有固体酸催化该反应存在的问题。通过分析介孔固体酸的烯基化催化性能数据并结合催化剂的表征结果，来揭示其构效关系。也将通过对微波和热化学下烯基化反应结果及反应前后催化剂特征变化的对比并结合微波场中固体酸温升特性考察，探究微波对介孔固体酸催化烯基化反应的强化作用及规律。本项目旨在为烯基芳香化合物的清洁生产奠定基础。