Mituła Katarzyna, Dutkiewicz Michał, Duszczak Julia, Rzonsowska Monika, Dudziec Beata
Faculty of Chemistry, Adam Mickiewicz University in Poznan, Uniwersytetu Poznańskiego 8, 61-614 Poznan, Poland.
Centre for Advanced Technologies, Adam Mickiewicz University in Poznan, Uniwersytetu Poznańskiego 10, 61-614 Poznan, Poland.
Polymers (Basel). 2020 May 6;12(5):1063. doi: 10.3390/polym12051063.
The scientific reports on polyhedral oligomeric silsesquioxanes are mostly focused on the formation of completely condensed T cubic type structures and recently so-called double-decker derivatives. Herein, we report on efficient synthetic routes leading to trifunctionalized, open-cage silsesquioxanes with alkenyl groups of varying chain lengths from -vinyl to -dec-9-enyl and two types of inert groups (iBu, Ph) at the silsesquioxane core. The presented methodology was focused on hydrolytic condensation reaction and it enabled obtaining titled compounds with high yields and purity. A parallel synthetic methodology that was based on the hydrosilylation reaction was also studied. Additionally, a thorough characterization of the obtained compounds was performed, also in terms of their thermal stability, melting and crystallization temperatures (TGA and DSC) in order to show the changes in the abovementioned parameters dependent on the type of reactive as well as inert groups at Si-O-Si core. The presence of unsaturated alkenyl groups has a profound impact on the application potential of these systems, i.e., as modifiers or comonomers for copolymerization reaction.
关于多面体低聚倍半硅氧烷的科学报告大多集中在完全缩合的T立方型结构的形成以及最近所谓的双层衍生物上。在此，我们报告了高效的合成路线，可得到具有从乙烯基到癸-9-烯基不等链长的烯基以及在倍半硅氧烷核心带有两种类型惰性基团（异丁基、苯基）的三官能化开笼倍半硅氧烷。所提出的方法侧重于水解缩合反应，并且能够以高收率和纯度获得目标化合物。还研究了基于硅氢化反应的平行合成方法。此外，对所得化合物进行了全面表征，包括其热稳定性、熔点和结晶温度（热重分析和差示扫描量热法），以显示上述参数随硅氧硅核心处反应性基团以及惰性基团类型的变化。不饱和烯基的存在对这些体系的应用潜力有着深远影响，例如作为共聚反应的改性剂或共聚单体。
