结构可控有机微孔易位聚合物的合成及催化性能研究

The development of microporous organic polymers (MOPs) with controllable structure will play an important role on their utility in catalytic reaction. Based on this background, we intend to synthesize PBI modified di-functional monomers, combine MCP, ADMET and MCP-ADMET methodology with self-assembly and hyper cross-linking strategy to develop size-tailored double-stranded polyacetylene, linear polyolefin and double-stranded polyacetylene bridged polyolefin, and then assemble into ladderphane, hollow cycle ring and nanofiber nanotopography respectively, further generate cross-linked microporous organic polymer network, and finally evaluation of their catalytic performance. According to estimate of the reaction behavior and kinetics of metathesis polymerization in different reaction media, and elucidation of the relationship between the topological structure of polymers and catalytic property of polymer-supported catalyst to master the efficient synthetic approach of functional polymers with designable nanostructures. The research will not only fabricate a novel class of MOPs with ordered structure, nanotopography and size tailorable, good thermos-stability, and high mechanical properties, but also master the matched information between monomers, metathesis methodology, polymer structures and catalytic performance, which will provide full and accurate evidence for further optimizing the structure and catalytic properties of the polymer supported catalysts. The research methods and polymer structures have some groundbreaking innovation which will provide a valuable reference for the development of new MOPs and their application in the field of catalytic materials.

发展结构可控的有机微孔聚合物，对于它们在催化反应中的应用具有重要的意义。基于此，本项目拟合成苝酰亚胺修饰的双官能单体，结合MCP、ADMET和串联式MCP-ADMET聚合反应，构建尺寸可裁剪的双缆聚乙炔、线形聚烯烃、双缆聚乙炔连接的桥形聚烯烃三类不同结构的聚合物，分别组装成梯蕃、中空环、纤维状纳米形貌并交联形成微孔有机聚合物网络，考察其负载金属催化剂的催化性能。通过不同反应介质中易位聚合反应规律和差异性的甑别、聚合物拓扑结构的构建和负载催化剂催化性能的研究，掌握合成纳米结构明确的聚合物的有效方法，研制出结构规整、形貌、尺寸可裁剪、热稳定性好、机械性能高的微孔聚合物，获得关于单体种类、聚合方法、聚合物结构与性能相互关系的信息，为进一步优化聚合物结构和催化性能提供翔实的依据。本项目旨在通过易位聚合和超交联丰富微孔聚合物的内涵，为开发性能优异的载体材料及其在催化领域的应用提供可行途径。

该项目基于PBI功能化双官能团二烯烃和二炔烃单体，结合ADMET、MCP、串联式MCP-ADMET反应及外交联“编织”法，成功合成了具有特殊形貌的易位聚合物并将其交联化，制备结构、形貌可控的MOPs。通过不同反应介质中易位聚合反应规律和差异性的甑别、聚合物拓扑结构的构建和负载催化剂催化性能的研究，掌握合成纳米结构明确的聚合物的有效方法，研制出结构规整、形貌、尺寸可裁剪、热稳定性好、机械性能高的微孔聚合物，获得了关于单体种类、聚合方法、聚合物结构与性能相互关系的信息，为进一步优化聚合物结构和催化性能提供翔实的依据。该项目通过易位聚合和超交联丰富微孔聚合物的内涵，为开发性能优异的载体材料及其在催化领域的应用提供可行途径。