冠醚基超交联聚合物催化CO_(2)与环氧化物的环加成反应  

Crown Ether-based Hypercrosslinked Polymers for the Cycloaddition of CO_(2) with Epoxides

作　　者：钟建交 罗荣昌 Zhong Jian-jiao;Luo Rong-chang(Huizhou Kaimeite Gases Co.,Ltd.,Huizhou 516000,China;School of Chemical Engineering and Light Industry,Guangdong University of Technology,Guangzhou 510006,China)

机构地区：[1]惠州凯美特气体有限公司,广东惠州516000 [2]广东工业大学轻工化工学院,广东广州510006

出　　处：《广东工业大学学报》2024年第2期122-128,共7页Journal of Guangdong University of Technology

基　　金：国家自然科学基金资助面上项目(21978056)。

摘　　要：CO_(2)与环氧化物通过环加成反应制备环状碳酸酯是CO_(2)资源化利用的有效途径之一,但工业上使用的传统催化剂往往存在着苛刻的反应条件和催化剂难以循环使用等缺点。开发能够使环加成反应在温和条件下发生的多相催化剂仍面临巨大挑战。通过Friedel-Crafts烷基化反应获得的超交联聚合物(Hypercrosslinked Polymer, HCPs)是一种具有永久孔隙率的三维网络,在CO_(2)催化转化方面具有极大的应用潜力。本文设计与合成了一种冠醚基超交联聚合物(CE-HCP-1)并将其成功地用于CO_(2)环加成反应中,分别使用两种工业催化剂(碘化钾KI或四丁基溴化铵TBAB)作为助催化剂时,均实现了在相对较温和无溶剂的条件下高效地合成系列环状碳酸酯。在KI/CE-HCP-1双组分催化系统中,在100℃和1.0 MPa的CO_(2)压力下,反应16 h,环氧氯丙烷的转化率可达90%以上,并且展现出良好的循环稳定性和底物适用性。因此,构建高效的双组分协同催化体系能为温和条件下CO_(2)的资源化利用提供良好的路径。The cycloaddition reaction of CO_(2) with epoxides to produce cyclic carbonates is one of the effective ways of CO_(2) resource utilization,but the traditional catalysts used in industry often have some disadvantages such as harsh reaction conditions and difficult recycling of catalysts.The development of heterogeneous catalysts that enable cycloaddition reactions to occur under mild conditions remains a major challenge.The hypercrosslinked polymer(HCPs)obtained by Friedel-Crafts alkylation reaction is a three-dimensional network with permanent porosity,which has great application potential in the catalytic conversion of CO_(2).In this research,a kind of crown ether-based hypercrosslinked polymer has been designed and synthesized and successfully used in the CO_(2) cycloaddition reaction.When two industrial catalysts(potassium iodide or tetrabutylammonium bromide)were used as co-catalysts,a series of cyclic carbonates have been synthesized efficiently under relatively mild and solvent-free conditions,showing good cyclic stability and substrate generality.In KI/CE-HCP-1 two-component catalytic system,the conversion rate of epichlorohydrin can reach more than 90%under 100℃and 1.0 MPa CO_(2) pressure for 16 h.Therefore,the construction of this efficient two-component co-catalytic system provides a good path for the resource utilization of CO_(2) under mild conditions.

关 键 词：超交联聚合物 冠醚 CO_(2) 环状碳酸酯 环加成 

分 类 号：TQ630[化学工程—精细化工]