环氧氯丙烷基脂肪族聚酯、聚碳酸酯接枝聚合物的制备和性能研究

This project aims to study on the graft copolymerization of aliphatic polyester and polycarbonate derived from the ring-opening copolymerization of cyclic anhydride with epichlorohydrin and carbon dioxide with epichlorohydrin respectively. Firstly, preparation of aliphatic polyester and polycarbonate from the ring-opening copolymerization of cyclic anhydride with epichlorohydrin and carbon dioxide with epichlorohydrin was investigated in detail. Second, the activies of chlorine in the backone of aliphatic polyester and polycarbonate was investigated to demonstrate the mechanism of graft copolymerization. Third, graft copolymers based on aliphatic polyesters and polycarbonates were prepared by atom transfer radical polymerization and nitroxide mediated living radical polymerization respectively. Based on the extensive study of copolymerization conditions, graft copolymers were prepared from aliphatic polyester and polycarbonate. Lastly, structure and properties of graft copolymers were investigated to improve the performance of aliphatic polyester and polycarbonate. It is important to explore the modification of alihaptic polyester and polycarbonate for controllable synthesis of graft copolymer, which are allow us to look forward to the high performance polymeric materials and accessible on an industrial scale in the future.

探索脂肪族聚酯、聚碳酸酯的改性方法具有重要的理论和研究意义。本项目旨在建立脂肪族聚酯和聚碳酸酯接枝共聚物制备方法。利用环氧氯丙烷/环状酸酐共聚酯、环氧氯丙烷/二氧化碳共聚碳酸酯，基于聚合物侧基氯原子活泼性，通过原子转移自由基聚合（ATRP）和氮氧稳定自由基聚合(TEMPO)反应制备脂肪族聚酯、聚碳酸酯接枝共聚物。设计小分子模型化合物，考察环氧氯丙烷/环状酸酐共聚物、环氧氯丙烷/二氧化碳共聚物侧基氯原子活性，探索和揭示共聚物引发ATRP聚合和TEMPO聚合反应机理。考察脂肪族聚酯、聚碳酸酯的ATRP和TEMPO接枝共聚合反应，确定接枝聚合反应条件，明确接枝聚合反应规律。研究脂肪族聚酯、聚碳酸酯接枝聚合物结构、性能，探索接枝聚合物应用。项目研究对于脂肪族聚酯、聚碳酸酯改性具有重要意义，拓宽接枝共聚合反应领域，为脂肪族聚酯、聚碳酸酯接枝共聚物可控制备提供理论依据。

接枝共聚合反应是一种有效方法实现脂肪族聚酯、聚碳酸酯的改性。本项目分别通过环氧氯丙烷和环状酸酐、环氧氯丙烷和二氧化碳共聚合制备多种脂肪族聚酯、聚碳酸酯，确定了聚合物侧基碳氯键断裂形成自由基的条件。利用脂肪族聚酯、聚碳酸酯侧基氯原子活性，通过热引发、光引发、氮氧稳定自由基、原子转移自由基接枝烯类单体共聚合反应，制备得到脂肪族聚酯、聚碳酸酯接枝聚合物，考察了接枝共聚合反应条件和接枝共聚物结构与性能。研究结果表明，环氧氯丙烷基脂肪族聚酯、聚碳酸酯侧基碳氯键能够断裂形成自由基，实现接枝烯类单体共聚合反应，制备得到高性能脂肪族聚酯、聚碳酸酯接枝共聚物。项目研究明确了环氧氯丙烷基脂肪族聚酯、聚碳酸酯侧基氯原子活性，建立了脂肪族聚酯、聚碳酸酯的接枝共聚合改性方法，为高性能脂肪族聚酯、聚碳酸酯的制备提供了理论和技术支持。