重氮乙酸酯的C1N2聚合反应研究

We will develop a novel type of polymerization reaction with diazoacetates as monomers in this project and the polymerized product is polyazomethane derivatives. The repeated unit in the backbone chain of the polymers from the reaction is -C-N=N- group, which is termed as C1N2 polymerization reaction. the C1N2 polymerization reaction is totally different from the well-known polymerization reactions such as olefinic polymerization, condensation polymerization, ring-opening polymerization as well as carbene polymerization in their monomer structures, polymerization mechanisms and polymer structures. The starting material for diazoacetates is glycin that is a natural product and thus petroleum resource is avoided. The idea about the C1N2 polymerization is originally created from the results of our previous investigation on the carbene polymerization with diazoacetate as carbene pool. The polymerization reaction systems, reaction conditions, polymerization mechanism, and stereochenmistry of the reaction will be carefully investigated, and its potential applications will also be evaluated.The selected activation of -C-N=N- group, the cis/trans linkage of repeated units and the optical performance of polyazomethanes are the new points in polymer chemistry. This project will open up an un-known field of polymerization reactions.

创建新的聚合反应类型是推进高分子化学发展的核心与基础，可开辟高分子化学研究的新领域。本项目拟以源自非石油资源的重氮乙酸酯为主要模型单体创建和发展C1N2三原子聚合反应新类型，这是申请者根据近年来自己的研究工作积累凝练而成，具有源头创新和原始创新性。C1N2三原子聚合反应在单体结构、聚合机理及聚合产物结构等方面与其他已知的聚合反应类型都存有显著差异，本项目将从筛选反应体系、优化反应条件、探讨反应机理、立体化学研究和拓展反应适用范围等五个方面系统深入地对该反应进行研究，将其发展成一类有重要应用领域和广阔应用前景的新聚合反应类型。C1N2聚合反应的单体选择性活化、重复结构单元形成聚合物主链时的顺/反键联方式、主链上偶氮基团可能导致聚合产物具有特殊的光学性能等都是对高分子化学的新贡献。本项目研究成果具有引领国际同行进入C1N2三原子聚合研究领域的潜力。

创建了重氮乙酸酯的C1N2共聚合反应，通过重氮乙酸酯C1N2聚合反应合成得到的C1N2共聚物分子可同时将太阳光谱中的紫外光和近红外光转换为可见光，为太阳光的高效率利用提供了新的方法学原理。发现了可以检测到C1N2结构单元的1,3-双自由基顺磁共振信号的新途径，在室温下检测获得了预期的金属-重氮自由基、金属-卡宾自由基和N↑1,C↑omega-双自由基的顺磁共振信号，为C1N2结构单元存在1,3-偶极子和1,3-双自由基互变异构的设想提供了直接检测证据，澄清了国际学术界延续了长达50余年的有关重氮乙酸酯1,3-双自由基结构形式的疑点。证实了1,3-偶极子、卡宾和烯烃这三种不同类的单体的共聚合反应可以通过N↑1,C↑omega-双自由基活性物种进行，不同取代基的重氮乙酸酯、卡宾和烯烃均可作为单体合成双向转换类型的荧光高分子。发现重氮乙酸酯与烯烃环化形成的吡唑啉可发生缩聚反应,聚吡唑啉亦具有上下转换发光性能。设计合成得到量子产率为51.8%的双吡唑啉聚合物。以甘氨酸为起始原料，经过重氮化、重氮乙酸酯的二聚、重氮乙酸酯和二聚体的环加成反应以及环加成产物的缩聚可以合成得到强荧光性聚吡唑啉，这是一类仅由一种氨基酸残基构成的荧光仿肽。还发现了重氮乙酸酯和顺丁烯二酸酐可以发生串联聚合反应。