POSS基多孔聚合物的设计合成及性能研究

Polyhedral oligomeric silsesquioxanes (POSS) has attracted wide attention for its use as building blocks to construct porous polymers through covalent bond linkage. In recent years, the applicant has conducted devoted research on POSS-based polymers where he developed a number of hybrid porous material systems, and has formed his own research specialties. Many unresolved problems still exist in this field, such as the synthesis POSS-based porous materials with crystalline structure and stimuli-responsive POSS-based porous materials. In this project, the applicant intends to design and synthesize new POSS monomers, such as boric acid and amine functionalized POSS monomers, and to use these monomers as precursors to construct some POSS-based porous materials with crystalline structures through dynamic covalent bonds. The applicant also proposes to synthesize some small molecule structural units with excellent pH and optical response, and introduce them to POSS-based networks via covalent bonds to produce POSS-based porous material which retains the corresponding pH and optical response. This project is a continuation and in-depth studies based on the applicant’s previous work.

笼型硅氧烷(POSS)作为构筑单元来来制备基于共建键连接的POSS基多孔材料是目前备受关注的一个研究方向。近年来，项目申请人在POSS基多孔材料方面做了较为深入和系统的工作, 发展了POSS基多孔材料的多个体系, 逐渐形成了自己的研究特色。目前，这一领域还存在一些热点问题和尚未解决的难点问题，例如：具有晶型结构的POSS基多孔材料，具有刺激响应的POSS基多孔材料等。针对以上问题，在本项目中，申请人拟设计合成一些新型的POSS单体，例如：硼酸功能化和胺基功能化POSS单体等，并以这些POSS单体作为前驱体通过动态共价键连接来制备具有晶型结构的POSS基多孔材料；项目申请人还拟分别合成一些具有pH和光学响应的小分子构筑单元，与POSS单体通过共价键连接来制备相应的具有pH和光学响应的POSS基多孔材料。本项目是申请人原有工作的延续和深入。

多孔材料因其能够满足现代社会高质量发展的需求而受到人们的极大关注。笼型倍半硅氧烷(POSS)是一类有机-无机杂化具有纳米笼型结构的硅氧烷化合物，组成为(RSiO1.5)n，其官能团的多样性和大骨架的结构特点使它十分适合通过共价键来构筑有机-无机杂化多孔材料。本项目中，我们对POSS基多孔材料进行了深入和系统的工作，发展了若干个POSS基多孔材料体系，形成了独特的研究风格。我们主要利用具有笼型结构的乙烯基POSS作为构筑单元，先后与平面分子、四面体分子、笼型分子和线性高分子等构筑单元进行拓扑组合，通过Heck偶合、Friedel–Crafts方式制备了系列POSS基多孔材料。我们还以乙烯基POSS为单一原料，开创了用阳离子聚合制备多孔聚合物的先例。我们进一步合成了一些新型的POSS单体，例如：咔唑功能化和三苯胺功能化的POSS单体，并分别通过氧化偶合和Scholl偶合反应制备了两种POSS基荧光多孔聚合物。此外，我们还利用不同的聚合方法和构筑单元对所制备的POSS基杂化多孔材料进行结构调控，分别得到微孔和介孔共存的双峰结构和多级孔结构的POSS基多孔材料。最后，我们研究了这些POSS基杂化多孔材料在离子和爆炸物检测、水处理等领域的应用。结果表明：POSS基多孔材料对有机染料和重金属离子具有极大的吸附和去除能力，在水处理领域具有极大潜力。总之，我们发展了系列POSS基杂化多孔材料，其制备方法简单，性能优异，得到国际学术界的高度关注和积极评价。