二氧化硫与天然单萜烯不对称、立体选择性交替共聚研究

Controlling emissions and effective utilization of SO2 have become the strategic research topic in various countries, and with the growing social demand for chiral products, efficient and green synthesis of chiral compounds has been paid more attention. Asymmetric copolymerization of olefin with SO2 is an effective approach for the preparation of chiral polysulfone, and for immobilization of sulfur, but the study still has not been considered. The fundamental reason is that the existing copolymerization of olefin with SO2 by free radical polymerization mechanism is difficult to control the structures of the copolymers and their copolymerization conditions. In this project, the coordination polymerization mechanism will be used. Using a series of polyaniline comlex( polyaniline is catalyst and carrier ) as catalysts prepared by supporting palladium, zinc and transition metal salt on chiral nano polyaniline/derivatives, high efficient and stable catalysts will be achieved for alternating copolymerization of SO2 with natural monoterpenes such as terpenes. The relationship between the polyaniline structure(metal ligand, chiral feature) and catalytic properties will be investigated. Effect of structures of polyaniline complex on molecular weight, molecular weight distribution, chain structures of the copolymer will be studied deeply. Especially, effects of the chirality of polyaniline and the optical activity of terpenes on the stereoselectivtiy of copolymers will be clarified. The relationship between the copolymer structure and biological properties (optical activity(rotation), antibacterial activity and biocompatibility) will be analyzed. The results provide a theoretical basis for preparation of chiral polysulfone from copolymerizaiton of the renewable monoterpenes with SO2.

控制SO2的排放并有效利用已成为各个国家的战略性研究课题,随着手性产品的需求日益增长，手性化合物的高效、绿色合成已备受关注。SO2与烯烃不对称共聚是制备手性聚砜及固硫的有效途径，然而其研究未引起重视。根本原因是现有烯烃与SO2共聚采用自由基聚合机理，其共聚条件苛刻、共聚物分子量低、结构难以控制。本项目采用配位聚合机理，以手性纳米聚苯胺/衍生物固载钯、锌及过渡金属盐系列聚苯胺配合物为催化剂（聚苯胺既是配体又是载体），实现高效、稳定地催化SO2与蒎烯等天然单萜烯不对称交替共聚，探讨聚苯胺的结构（金属配位方式、手性特征等）与催化性能的关系；深入研究聚苯胺配合物的结构对共聚产物的分子量、分子量分布、链结构的影响，特别阐明手性聚苯胺/单萜烯的旋光特征对共聚产物立体结构的影响规律；分析共聚产物结构与生物特性（旋光、抗菌及生物相容）之间的关系。结果为从可再生萜烯资源固定SO2制备手性聚砜提供理论依据。

控制SO2的排放并有效利用已成为各个国家的战略性研究课题。烯烃/环氧化物与SO2催化共聚制备聚砜或聚亚硫酸脂是利用SO2的有效途径之一。但现有烯烃/环氧化物与SO2共聚采用自由基聚合机理，其共聚条件苛刻、共聚物分子量低、结构难以控制。本项目采用配位聚合机理，以手性纳米聚苯胺/衍生物固载Salen及过渡金属盐系列聚苯胺配合物为催化剂（聚苯胺既是配体又是载体），实现了高效、稳定地催化SO2与蒎烯等天然单萜烯不对称交替共聚，探讨了聚苯胺的结构（金属配位方式、手性特征等）与催化性能的关系；深入研究了聚苯胺配合物的结构对共聚产物的分子量、分子量分布、链结构的影响；分析了共聚产物结构与其热稳定性、光学性能等性能之间的关系。相关研究结果发表学术论文20篇，SCI14篇，EI6篇。培养博士研究生1名，硕士研究生7名。