改进型Wolff环缩合在含1,2,3-三氮唑高分子合成中的应用

Recently, polymers containing 1,2,3-triazole moieties have been receiving increasing attends due to their potential applications in the field of separation membranes, engineering plastics, biomedical devices, and organic optoelectronic materials. In this proposal, we purpose to synthesize a variety of 1,2,3-triazole-containing polymers through three pathways based on modified Wolff’s cyclocondensation reactions, using α-diazo-β-oxoamides and primary amines as the staring materials. Then the properties of these multi-substituted 1,2,3-triazole-containing polymers will be systematically characterized. The approaches to 1,2,3-triazole-containing polymers in this proposal enjoy not only the advantages of traditional Wolff’s 1,2,3-triazole synthesis such as high regioselectivity, abundant raw materials, and the possibility multi substitutions, but also the virtues of frequently-used click chemistry based on organic azides and terminal alkynes including high yields and feasibility. The accomplishment of this project will lay scientific foundation for the applications of 1,2,3-triazole-containing polymers as functional materials.

由于在分离膜、特种工程塑料、生物医用高分子、有机光电材料等领域都具有潜在的应用前景，含1,2,3-三氮唑结构的高分子近期得到了广泛关注。本项目拟从单体设计角度出发，通过改进型Wolff环缩合反应，采用α-重氮乙酰乙酰芳胺和各种伯胺作为原料，通过三种途径分别制备含1,2,3-三氮唑的功能高分子，并进一步研究此类含多取代1,2,3-三氮唑结构的高分子的功能特性。此方法不仅具备了传统Wolff制备1,2,3-三氮唑的高区域选择性、原料丰富易得及多取代基团等优点，并且还具备了常用的通过有机叠氮与炔的“点击化”反应制备1,2,3-三氮唑的高产率、反应操作简单等优点。本项目的顺利实施将为含1,2,3-三氮唑结构的聚合物在功能高分子中的推广应用奠定了科学基础。

在本项目支持下，我们以α-重氮-1，3-二羰基化合物为基础原料，通过合理的聚合路线设计，分别实现了三类高分子的合成：（1）侧链上含1，2，3-三氮唑类高分子的合成，这类高分子兼具聚苯乙烯的芳香性、聚乙烯基吡啶的极性及聚丙烯酸酯的可修饰性；（2）壳聚糖接枝1，2，3-三氮唑高分子的合成，这类高分子在医药材料领域有着潜在的应用；（3）严格交替型聚酯的制备，我们的方法克服了传统合成这类高分子所需的条件苛刻、分子量低及原料昂贵等缺点。除此之外，我们还发展了几种有效合成有机小分子的方法，主要包括：炔烃的氰氨化反应、多取代吡唑类化合物的合成、喹啉类化合物的还原及叠氮基醇类化合物的还原性半嚬哪醇重排反应等。