氨基酸衍生O-羧基环内酸酐（OCA）的可控开环聚合是制备功能化脂肪族聚酯的重要途径。然而，在现有的催化体系下，通过该方法合成高分子量（Mn>200 kDa）立构规整的功能化脂肪族聚酯仍然面临着巨大的挑战。本项目期望借鉴细胞膜内氯离子传输的化学本质，设计与合成一类基于硫脲-吡啶衍生碱结构的阴离子结合有机协同催化剂，通过阴离子结合作用来抑制OCA单体的消旋以及伴随的不利副反应，同时保持高效、可控的链增长得到高分子量等规聚合物；在此基础之上，构筑大位阻阴离子结合有机协同催化体系，通过链末端控制机理来实现外消旋OCA单体的立体选择性聚合；最后，通过这些催化体系制备结构丰富的脂肪族聚酯，深入研究这类聚合物的链结构与性能之间的关系，为进一步合成功能化聚酯材料提供理论指导。这种新的催化聚合理念在抑制不利副反应、实现高效聚合等方面具有普适性，可以被推广到其它的聚合研究中，具有十分重要的研究意义。

Controlled ring-opening polymerization (ROP) of amino acids-derived O-carboxyanhydrides (OCA) is an important approach towards functionalized aliphatic polyesters. However, ROP of OCA to synthesize high molecular weight (high MW, Mn>200 kDa) stereoregular polyesters via current catalytic systems still faces formidable challenges. In this proposal, we anticipate to imitate the chemical nature of chloride anion transport in cytomembrane, and devise a class of anion-binding synergetic organocatalysis based on thiourea/pyridine derivant for ROP of OCA, which well addresses the racemization and accompanying side reactions, while maintaining efficient and controlled chain propagation to obtain high MW isotactic polymers. On this basis, further build bulky groups in anion-binding synergetic organocatalysts to implement stereoselective ROP of racemic OCA via chain-end-control mechanism. Finally, through these catalytic systems, rich aliphatic polyesters will be prepared, and the relationship between the chain structure and properties of such polymers will be thoroughly studied to provide theoretical guidance for the further synthesis of functional polyester materials. This new catalytic-polymerization concept to suppress detrimental side reactions and to facilitate the chain propagation is universal and valuable, and can be extended to other polymerization studies.