基于后交联法的HCPs的设计合成及其气体吸附性能

Since the limitation of the synthesis method of traditional post crosslinked method, the structure of the monomer and the polymer has been restricted. It has a great effect on the design, Synthesis and properties of new functional hypercrosslinked microporous organic polymers (HCPs). This project will construct directly the hypercrosslinked polymer networks containing carbonyl functional groups, thiophene functional units and functional units of macrocyclic compounds with the post crosslinked method combining the modern organic synthesis method of metal participation and the classical Wilimoson etherification method based on the design of a series of multifunctional thiophene monomer compounds. The crosslinked reaction will be investigated with infrared absorption spectroscopy, nuclear magnetic resonance spectroscopy and elemental analysis. The thermal stability and the solid morphology of HCPs will be studied with thermogravimetric analysis and SEM, respectively. Based on the further investigation of the gas adsorption properties of HCPs, the synergistic effect of the functional groups of carbonyl groups and the functional units of macrocyclic compound and thiophene on the adsorption properties of HCPs will be researched. The effect of the position of macrocyclic compounds on the adsorption behavior of HCPs will be proved. Thus the mechanism of the novel post crosslinked reaction will be proved and the relationship between the structure of the functional HCPs and the gas adsorption properties will be verified. The implementation of this project will provide new means and method for the synthesis of functional HCPs and lay the theoretical foundation for the design and explore of novel high-performance HCPs.

传统后交联法由于合成方法的局限性，造成了目前单体和聚合物结构的有限性，限制了新型功能性超交联聚合物（HCPs）的开发和利用。本项目拟通过系列功能性噻吩类单体的设计，运用基于金属参与的现代有机合成反应方法Stille缩合聚合与经典的Wilimoson成醚反应相结合的新型后交联法，构筑同时含有酮羰基功能基团、噻吩和大环化合物功能性单元的功能性HCPs。红外吸收光谱、核磁共振光谱、元素分析研究交联反应，热失重分析和扫描电镜研究HCPs的热稳定性能和固体形貌，在进一步对HCPs气体吸附性能研究的基础上，研究酮羰基功能基团、大环化合物和噻吩功能性单元对HCPs吸附性能的协同作用规律，探明大环化合物在聚噻吩链间的位置对HCPs吸附性能的作用规律，从而探明后交联反应机制，探明HCPs的结构与气体吸附性能的关系规律。为新型功能性HCPs的合成提供新的手段和方法，为高性能HCPs的设计开发奠定理论基础。

新型功能性超交联聚合物（HCPs）的开发和利用有赖于新型合成方法的发展。本项目通过系列功能性噻吩类单体的结构设计，对基于金属参与的现代有机合成反应方法Stille缩合聚合与经典的Wilimoson成醚反应相结合的新型后交联法进行研究，构筑了同时含有酮羰基功能基团、噻吩和大环化合物功能性单元的功能性HCPs。红外吸收光谱、核磁共振光谱、元素分析等手段对聚合物的结构进行了表征。实验证明了金属参与的现代有机合成方法与经典交联方法相结合的新型后交联法合成超交联聚合物的可行性。通过热失重分析和扫描电镜研究了HCPs的热稳定性能和固体形貌，重点研究了HCPs的气体吸附性能、铜离子吸附性能和染料罗丹明的吸附性能，探明了研究酮羰基功能基团、大环化合物和噻吩功能性单元对HCPs吸附性能的协同作用规律，为新型功能性HCPs的合成提供新的手段和方法，为高性能HCPs的设计开发奠定理论基础。并针对项目进行过程中遇到的无水无氧反应装置的问题，进行了一系列新型实验装置的研发，为研究的顺利快速进行奠定了基础。