Preparation of Tri(alkenyl)functional Open-Cage Silsesquioxanes as Specific Polymer Modifiers

Abstract

The scientific reports on polyhedral oligomeric silsesquioxanes are mostly focused on the formation of completely condensed T8 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.

Slick Synthetic Approach to Various Fluoroalkyl Silsesquioxanes—Assessment of their Dielectric Properties

“…The chemicals were purchased from the following sources: Sigma-Aldrich (St. Louis, MO, USA) for toluene, chloroform-d, chloroform, Karstedt's catalyst-2% xylene solution [Pt 2 (dvs) 3 )] and silica gel 60. The following silsesquioxanes, monoT 8 SiH, monoT 8 SiVi, triT 7 SiH, triT 7 SiVi, DDSQ-2SiH, DDSQ-2SiVi, DDSQ-2OSiVi, DDSQ-4OSiH, DDSQ-4OSiVi, octaT 8 SiH and octaT 8 SiVi, were prepared according to the literature procedures [59][60][61] and so was the olefin CH 2 =CHCH 2 OCH 2 (CF 2 ) 3 CHF 2 (F1) and silane HSiMe 2 OSiMe 2 CH 2 CH 2 CH 2 OCH 2 (CF 2 ) 3 CHF 2 (F5) [62,63]. All solvents were dried over CaH 2 before use and stored under argon over 4Å molecular sieves.…”

Cagelike Rb2-, K2-, and Na2-Tetracopper(II) Silsesquioxanes with Quaternary Ammonium Cations: Synthesis, Structures, and Catalytic Activity

“…Silsesquioxanes [RSiO 1.5 ] n are popular building blocks for generating a variety of new molecules and functional materials. − Their examples include three-dimensional emulsifiers, surface modifiers, nanofillers, hydrogen-bonding catalysts, atomic oxygen resistant composite films, and monomers for copolymerization . Another important feature of partly condensed silsesquioxanes is an ability to serve as ligands for various cage metalladerivatives. − The vast structural variety of cagelike metallasilsesquioxanes (CLMSs) endows them with a bunch of practically important properties, e.g., photophysical − or magnetic, , including single molecule magnets and spin glasses .…”

Acetone Factor in the Design of Cu4-, Cu6-, and Cu9-Based Cage Coppersilsesquioxanes: Synthesis, Structural Features, and Catalytic Functionalization of Alkanes

“…The investigation of partly condensed POSS is also appealing, leading to the design of new monomers for copolymerization reactions, H-bond donor catalysts, OLED’s emission layers, three-dimensional emulsifiers, different films (e.g., transparent, scratch resistant, self-healing, or Langmuir–Blodgett/Langmuir–Schaefer films), and spin-on-glass networks with ultralow dielectric constants . By design, partly condensed polyhedral silsesquioxanes can be also regarded as versatile ligands for the construction of various cagelike metallacomplexes. − These intriguing compounds attract significant interest for the potential removal of radioactive elements, fabrication of flame retardants, − biomedical agents, luminescent materials, , or molecular magnets .…”