二氧化碳基聚碳酸酯-聚酯立构嵌段共聚物的构筑与性能研究

The project is devoted to the constructions of carbon dioxide-based polycarbonate-polyester stereoblock copolymers, which contain different geometric polyester segments in their backbones. The geometric stereo polyester will be obtained by applying desymmetrization of meso-anhydride by nucleophilic ring opening using bulky alkoxide anion resulting in enantiomerically enriched compounds.The most attentions are paid on that the effects of geometric configuration of polyester segment on the properties of carbon dioxide-based polycarbonate in this study. In addition,the influence on performance of block copolymer via the chemical composition and molecular weight of polyester chain segment will also be investigated in detail. As a result, structure-activity relationship between composition and properties can be achieved. The successful implementation of this project is very valuable not only in the development of tuning method for the CO2 based polycarbonate performances, but also in the evolution of synthetic methodology in polymer chemistry. The research results will afford theoretical and experimental support for building carbon dioxide-based polycarbonate materials with special structure or high performance.

本项目致力于含有不同几何异构的聚酯链段的二氧化碳基聚碳酸酯-聚酯立构嵌段共聚物的构筑，利用内消旋酸酐在大位阻烷氧基的亲核进攻下发生选择性开环得到立体有择的对映体产物这一有机合成策略运用到几何立构聚酯的获得上。重点研究聚酯链段的几何构型对二氧化碳基聚碳酸酯性能的影响，同时考察聚酯链段的化学组成以及分子量的大小对嵌段共聚物性能的影响，在此基础之上获得组成与性能之间的构效关系。本课题的成功实施无论对二氧化碳基聚碳酸酯的性能调控方法的发展还是在高分子合成方法学的研究上都极具价值，其研究结果将为获得新性能或结构特殊的二氧化碳基聚碳酸酯材料提供理论和实践支持。

本项目致力于构筑立体异构的二氧化碳基聚碳酸酯-聚酯嵌段共聚物，将内消旋酸酐在大位阻烷氧基的亲核进攻下发生选择性开环得到立体有择的对映体产物这一有机合成策略运用到几何立构聚酯的获得上。1）采用顺序加料方式制备了由CO2基聚碳酸酯和具有不同立体构型聚酯构成的聚酯-聚碳酸酯嵌段共聚物；2）发现CO2能够抑制聚酯段发生cis-(exo, exo)或cis-(endo, endo)向trans-(exo, endo)的构型转变，在PPNCl催化exo-NA与过量CHO反应中通入CO2几乎得到了完全为cis-构型的聚酯；3）探讨了DMAP/CHO催化聚酯-聚碳酸酯嵌段共聚物的降解。聚酯段在降解过程中发生由cis向trans立体化学构型转变，此转变过程同样可以通过CO2进行调控；4）制备了几种结构新颖的金属、双核金属配合物，研究了它们在环氧化合物与CO2 聚合反应中活性和选择性的构效关系，对所得的聚合物双键侧链进行功能化修饰，改善了聚合物性能。5）制备了含硫的pH和ROS双响应性的两亲性聚β硫酯化合物，考察其自组装及解散行为，并且在MCF-7细胞中对抗癌药物阿霉素的释放进行了验证。