基于二氧化碳与双环氧化合物共聚一步制备线性功能化聚碳酸酯的研究

The preparation of polycarbonate derived from the copolymerization of carbon dioxide and epoxides has been drawn extensive attentions due to its high value-added usage of carbon dioxide. However, the flaws of thermodynamic properties for both poly(propylene carbonate) and poly(cyclohexene carbonate) and the absence of functional group for further chemical modification as well as hydrophobic nature greatly limit their applications on a large scale. This project is devoted to the synthesis of epoxy (EP) and cyclocarbonate (CC)-functionalized polycarbonate (APC) via the copolymerization of carbon dioxide with diepoxides in one pot. The effects of nature of epoxy ring of diepoxides, catalyst structure and reaction parameters on the product selectivity, controllable incorporation of pendant functional group and molecular weight of resultant APC will be investigated in detail. Multi-level regulation of polymer structure and performance can be further obtained via the incorporation of new functional groups resulting from the tunable transformation reaction of EP and CC functional groups. This research provides the good material basis for achieving the high value-added CO2-based APC and extending its applications. Importantly, this project affords a new strategy for the improvement of properties of CO2-based APC, and offers a green and simple approach to prepare functional APC.

二氧化碳(CO2)和环氧化合物共聚制备脂肪族聚碳酸酯(APC)是一种备受关注的高值化利用CO2的方法，然而目前研究最多的聚丙撑碳酸酯和聚环己烯碳酸酯在热力学性能的一些不足以及疏水和缺少可修饰的官能团，极大地限制了其规模化应用。本项目旨在利用CO2与双环氧化合物“一步”制备侧链含有环氧(EP)基团或/和环状碳酸酯(CC)基团的线性功能化APC。探索构成双环氧化合物的环氧环的性质、催化剂结构、聚合条件与产物选择性、侧链功能基团的可控引入和聚合物分子量之间的关系。在此基础之上，研究聚合物侧基上EP和/或CC官能团的可控转换，引入新的功能基团，实现对CO2基APC结构性能的多层次调控，为CO2基APC的高附加值化和拓宽其应用提供良好的材料基础。本研究为CO2基聚碳酸酯性能改进和功能化提供新的途径，也为功能化APC的合成提供一种绿色、简捷的新方法。

本项目分别利用端环氧和内环氧与二氧化碳反应时的反应活性和产物选择性的不同和取代基的电子效应对产物选择的不同，实现了二氧化碳与双环氧化合物“一步”制备侧链含有环氧基团或/和环状碳酸酯基团的线性功能化脂肪族聚碳酸酯。本研究为二氧化碳基聚碳酸酯性能改进和功能化提供新的途径，也为功能化APC的合成提供一种绿色、简捷的新方法。其次开展了双核[OSSO]的Zn、Cr配合物在二氧化碳与环氧化合物环加成反应、己内酯开环聚合以及环氧化合物与酸酐共聚制备聚酯研究，初步阐明了催化剂结构与催化行为之间的关系，提出了可能的反应机制。除此之外，我们提出了一种高熵微区互锁的全固态聚合物电解质（ASPEs）的设计思路，赋予ASPEs优异的韧性、适当的离子电导率、高的阳离子迁移数(0.63)和良好的热稳定性(Td > 400 °C)。