双缆共聚物的多重极化和高介电储能性

It is a key issue for the research of dielectric materials by developing the high dielectric and energy storage polymers, and therefore this project will be focused on the fundamental studies about the novel insulating/conductive double-stranded block copolymer with tailored component and structure, synthesized by the tandem metathesis cyclopolymerization and ring-opening metathesis polymerization (MCP-ROMP) of the strong dipolar m-(trifluoromethyl)phenyl groups-contained bis(1,6-heptadiyne) and bisnorbornene connected by covalent bond or phenanthroline-metal ion coordination bond for enhancing the dielectric and energy-stored properties. By introducing the strong electron-withdrawing group, ionic group, metal ion, and conjugated chain structure, the actions of dipole polarization, ionic polarization, electronic polarization, and atom polarization from different functional units should be strengthened. Further integrating the positive contribution from the nano-scaled interfacial polarization of core-shell interface and asymmetric space structure, the obviously increase in dielectric and energy-stored properties may be achieved. It is expected to obtain a novel type of nanodielectric materials based on the double-stranded stereoregular block copolymer with good film-forming property and stability, high dielectric constant, low dielectric loss, outstanding electric field strength, and excellent stored/released energy density. The study is aimed at erecting the generally adaptability of combined ROMP-MCP method, which would be a valuable strategy for establishing a novel family of double-stranded block copolymer, and finally to provide full and accurate evidence for finely control over the stereoregularity and dielectric properties. It has the high academic value and strongly applied prospect for enriching and developing the researched new field in metathesis polymerizations and nanodielectric materials.

研究新型聚合物的高介电储能性，是介电材料领域的一个热点。本项目拟设计基于强极化苝酰亚胺桥联基团共价连接和菲罗啉-金属离子配位连接的双官能环烯烃和二炔烃单体，利用串联式易位环化聚合和开环易位聚合方法，制备结构和分子量可裁剪的绝缘/导电型双缆嵌段共聚物，开展对聚合物介电储能性增强的基础研究。通过在聚合物链上引入强极性基团和三种不同的离子基元，融合四种或五种极化作用，并构筑明确的纳米结构，以期获得一类成膜性和稳定性好、力学性能强、介电常数高、介电损耗低、耐电场强度和能量密度卓越的有规立构双缆嵌段共聚物，为开发高储能密度薄膜电容器提供纳米介电新材料。本项研究旨在创新高分子合成方法和丰富新型结构的介电聚合物材料体系，具有重要的学术价值和科学意义。

研究聚合物的介电储能性，是介电材料发展的一个新方向。本项目设计合成了几种单官能环烯烃和二炔烃单体以及共价和配位连接的双官能环烯烃单体，通过可控性好的开环易位聚合和易位环化聚合反应，制备得到了含多重极化单元的单缆、双缆嵌段共聚物，创建了端位和侧位络合金属的两种双缆聚合物结构类型，分别络合了钌、铱、铬三种金属离子，拓展了络合金属的环形共聚物的合成方法，构建了明确的纳米结构，掌握了绝缘-导电型、单缆、双缆嵌段共聚物和金属掺杂的环形聚合物的合成技巧，丰富了易位聚合物合成和介电储能性研究体系和研究内涵。通过融合不同功能基元的偶极极化、离子极化、界面极化和电子极化等多重要素，有效调控了单缆、双缆嵌段共聚物的介电储能性，获得几种成膜性好、介电常数高（ > 30）)、介电损耗低（˂ 0.02）、耐电场强度（> 400 MV m-1）和能量密度（> 5 J cm-3）高的嵌段共聚物纳米介电新材料，为进一步优化聚合物组成、结构、形貌和介电性储能性指标提供了翔实的依据，为增强对聚合物介电储能性调控的认识提供了有益指导。