Development of Green Sustainable and Radical-Chain Degradable Polymer Materials

研究了在常压下1,3-二烯单体与分子氧自由基选择性共聚制备可降解聚过氧化物的简便方法。介绍了聚过氧化物的共聚机理、降解行为、功能聚过氧化物的合成及其应用。多过氧化物的降解可通过加热、紫外线照射、胺氧化还原反应和酶反应等多种刺激发生。采用1,3-二烯单体与氧直接共聚和前体聚过氧化物官能化两种方法合成了多种功能性聚过氧化物。水溶性多过氧化物在降解温度下表现出可逆的LCST。开发了将二烯基引入前驱体聚合物的多种方法。利用得到的二烯基功能化聚合物制备降解过程中热演化小的可降解网状聚合物和可降解支链共聚物，研究降解前后微相分离结构的变化。探讨了聚过氧化物的实际应用。

We developed facile synthesis of degradable polyperoxides by the radical alternative copolymerization of 1,3-diene monomer with molecular oxygen at atmospheric pressure. We revealed copolymerization mechanism, degradation behavior, the synthesis of functional polyperoxides, and the application of functional polyperoxides. Degradation of polyperoxides occurred by various stimuli such as heating, UV irradiation, redox reaction by amines, and enzyme reaction. Various functional polyperoxides were synthesized by two methods, i.e., the direct copolymerization of functional 1,3-diene monomers with oxygen and the functionalization of precursor polyperoxides. Water soluble polyperoxides reversibly showed LCST under degradation temperature. Versatile methods to introduce dienyl groups into precursor polymers were developed. The resulting dienyl-functionalized polymers were utilized to prepare degradable networked polymers with small heat evolution during degradation and degradable branched copolymers to study their microphase-separated structure change before and after degradation. The practical application of polyperoxides were also investigated.