含MOSS 的有机-无机杂化高分子的制备及其结构与性能研究

Stereoregular oligomeric silsesquioxanes have been emerging as a class of important building blocks for inorganic-organic hybrid materials. The Si/O structural untis can be incorporated into organic polymers to obtain novel organic-inorganic nanocomposites with improved properties. The improvement in properties for the organic-inorganic hybrids can be attributed to the follwing two elemental and structural features of stereoregular oligomeric silsesquiocanes: i) organic-inorganic hybrid assembly with reactive (or/and functional) ligands and ii) rigid stereoregular nanostructures. In the past years, polyhedral oligomeric silsesquioxanes (POSS) have been extensively investigated. Nonetheless, the preparation of POSS macromers on a large scale is still a challenging task for the time being. It is long a pursuit to explore to obtain the materials silimar to POSS with facile approaches. Macrocyclic oligomeric silsesquioxanes (MOSS) is a class of novel stereoregular oligomeric silsesquioxanes, which are derived from polyhedral oligoalkylmetallasiloxanes with satisfactory yields. From elemental points of view, MOSS macromers possess the features similar to POSS. Nonetheless, MOSS macromers possess stereoregular macrocyclic structure, which are quite different from the cage-like structure of POSS. In the past years, MOSS molecules were prepared only for the purpose of structural analysis of the polyhedral oligoalkylmetallasiloxanes crystals. To the best of our knowledge, there are only a few reports on the preparation of organic-inorganic hybrids by the use of MOSS macromers. In this project, we proposed to utilze MOSS as building blocks to preopare the organic-inorganic hybrids. In this project, we firstly explored to synthesize a variety of functionalized MOSS macromers,which are avalaible to prepare the MOSS-containing organic-inorganic hybrids. Thereafter, the structures and properties of this class of hybrids were investigated. The key issues to be solved in this projects are : i) to eastablish the preparative methodology of MOSS macromers, ii) to investigate the structures and properties of MOSS-containing polymers, iii) to control the microstructures of MOSS-containing polymer nanocomposites.

大环齐聚倍半硅氧烷(Macrocyclic Oligomeric Silsesquioxnes, MOSS)是一类新型齐聚倍半硅氧烷，由金属-齐聚倍半硅氧烷络合物的硅醚化反应制得。MOSS 的结构式为[RSiO1/2]n，具有有机-无机杂化的元素特征及纳米尺度上的刚性大环结构。在申请中，我们建议将MOSS 用作高分子在纳米尺度上微结构的构筑单元，制备一类新型的有机-无机杂化高分子。在本工作中，我们将合成与表征一系列具有不同大环尺寸、含有不同R基团的MOSS，通过对这些MOSS 分子进行化学修饰使之功能化；采用各种不同路线将MOSS 引入有机高分子中。我们将利用MOSS 的空间立体结构特征，制备具有不同拓扑结构的大分子。充分利用含MOSS大分子拓扑结构及自组装特性控制高分子在纳米尺度上的微结构的形成，实现有机高分子的高性能化，在此基础上建立这一类有机-无机杂化高分子的结构与性能关系。

在本课题研究工作中， 我们合成了一系列大环齐聚倍半硅氧烷(Macrocyclic Oligomeric Silsesquioxnes, MOSS)，并将MOSS引入有机高分子体系中，制备了一系列新的有机-无机杂化高分子材料并对其结构与性能之间的关系进行了深入细致的研究。 在本课题研究工作中，我们合成了一系列具有不同大环尺寸、含有不同R 基团的MOSS，并对这些MOSS 分子进行化学修饰实现了功能化；通过采用各种不同路线，成功地将MOSS 引入有机高分子中。利用MOSS 的空间立体结构特征，制备了一系列具有不同拓扑结构的有机-无机杂化大分子，并充分利用含MOSS 大分子拓扑结构及自组装特性控制高分子在纳米尺度上的微结构的形成，实现有机高分子的高性能化，在此基础上建立了这一类有机-无机杂化高分子的结构与性能关系。在本项目研究过程中，我们还研究了与MOSS相关的另一类具有结构精确可控的二官能度齐聚倍半半硅氧烷，即双甲板型齐聚倍半硅氧烷(Double Decker Silsesquioxanes, DDSQ)，我们研究了DDSQ的制备、功能化以及将DDSQ引入高分子主链获得新型的有机-无机杂化高分子，在此基础上深入研究了其结构与性能。