离子液体－多功能催化剂体系构筑及其催化转化生物质基芳香醚制备酮类化合物的研究

Methyl substituted ketones are important raw materials in chemical industry and intermediates in organic synthesis. Utilization of biomass-derived aromatic ethers to produce ketones is of great theoretical and practical significances. However, such catalytic reaction involves both transalkylation and catalytic hydrogenation of benzene ring, which has not been reported. With respect to this problem, in this project, a series of multifunctional catalysts with catalytic functions of transalkylation and catalytic hydrogenation, including solid acids (such as Y zeolite, ZSM-5 zeolite, etc) supported metal (such as Pd, Pt, Ru, Rh, Fe, Co, Ni, etc）catalysts, will be designed and prepared. Acidic and neutral functional ionic liquids will be designed and screened. On this basis, ionic liquid-multifunctional catalyst systems will be designed and prepared. The rules and mechanisms of activation, cleavage and transmethylation of C-O bond in the aromatic ethers will be studied systematically in the catalytic conversion of biomass-derived aromatic ethers into ketones. The rules and mechanisms of activation and catalytic hydrogenation of benzene ring will be studied systematically, too. Coordination effects of ionic liquid and catalyst, catalytic mechanism and solvent effect of the reaction, will be discovered within the ionic liquid-multifunctional catalyst system. New methods and pathways of catalytic conversion of biomass-derived aromatic ethers into ketones will be developed. This research will lay the foundation for the conversion and utilization of biomass.

含甲基取代基的酮类化合物是重要的化工原料和有机合成中间体。用生物质基芳香醚化合物制备酮类化合物具有重要的理论和实际意义。然而，此类反应同时涉及烷基转移反应和苯环催化加氢反应，目前尚未见报道。针对这一难题，本项目将设计制备一系列同时具有催化烷基转移反应和苯环催化加氢反应的多功能催化剂，包括固体酸（如Y型、ZSM-5型等）负载金属催化剂（如Pd、Pt、Ru、Rh、Fe、Co、Ni等），设计和筛选酸性、中性的功能性离子液体。在此基础上构筑离子液体－多功能催化剂体系。系统研究生物质基芳香醚催化转化制备酮类化合物过程中芳香醚中碳氧键的活化、断裂、甲基转移规律和机理，以及苯环结构的活化、催化加氢规律与机理，揭示离子液体－多功能催化剂体系中离子液体与催化剂之间的匹配及协同作用规律，催化反应机理和反应的溶剂效应，发展生物质基芳香醚化合物催化转化制备酮类化合物的新方法和新途径。为生物质转化利用奠定科学基础。

酚类、芳烃类和有机酸类化学品是重要的化工原料和有机合成中间体。用可再生的木质素碳资源制备高附加值化学品具有重要的理论和实际意义。然而，此类反应同时涉及木质素分子结构中的碳-碳和碳-氧键活化、转化反应，目前仍处在起步阶段。针对这一难题，项目组设计制备了一系列同时具有催化碳-碳和碳-氧键转化反应的多功能催化剂，包括固体酸（如Y型等）、固体酸负载金属催化剂（如Ru、W等）和水溶性Lewis酸等。同时，设计和筛选了酸性、中性的功能性离子液体、有机溶剂和水等反应介质。在此基础上构筑了绿色溶剂－多功能催化剂体系。系统研究了木质素碳资源催化转化制备酚类、芳烃类和有机酸类化学品过程中木质素分子结构中碳-氧键的活化、断裂规律和机理，以及碳-碳键的耦合规律与机理，揭示了绿色溶剂－多功能催化剂体系中反应介质与催化剂之间的匹配及协同作用规律，催化反应机理和反应的溶剂效应，开发了一系列催化木质素碳资源转化制备高附加值化学品的新方法和新途径，为生物质转化利用奠定了科学基础。