Soluble network polymers based on trifluoropropyl‐substituted open‐cage silsesquioxane: Synthesis, properties, and application for surface modifiers

Abstract

Fluorinated completely condensed polyhedral oligomeric silsesquioxanes (F-CC-POSSs) are widely utilized as surface modifiers for polymeric materials because of their polyhedral and fluorine-rich structures, which generate polymers with lower surface energies under molecular-level control. In contrast, their derivatives, fluorinated incompletely condensed or open-cage POSSs (F-IC-POSSs), have similarly intriguing structures, but their utilization for polymer synthesis remains undeveloped. Herein, fluorinated network polymers were prepared based on a 3,3,3-trifluoropropyl-substituted IC-POSSs via hydrosilylation polymerization with isobutyl-and phenyl-substituted IC-POSS under optimized conditions. In addition to their good thermal stability and tunable refractive indices, these polymers exhibited solution processability and their casting films showed excellent optical transparency, indicating their potential for constructing fluorinated polymers. Their utilization as surface modifiers was examined by addition to poly(methylmethacrylate) (PMMA) films. Intriguingly, modified PMMA films with 2.0 and 0.5 wt% addition showed similar hydrophobicity and surface energies to the films prepared with only fluorinated network polymers.

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 .…”

“…Silsesquioxanes [RSiO 1.5 ] n are popular building blocks for generating a variety of new molecules and functional materials. 1−7 Their examples include three-dimensional emulsifiers, 8 surface modifiers, 9 nanofillers, 10 hydrogen-bonding catalysts, 11 atomic oxygen resistant composite films, 12 and monomers for copolymerization. 13 Another important feature of partly condensed silsesquioxanes is an ability to serve as ligands 14 for various cage metalladerivatives.…”

Alkenyl-Functionalized Open-Cage Silsesquioxanes (RSiMe2O)3R′7Si7O9: A Novel Class of Building Nanoblocks

“…In our experiments, we used commercially available platinum catalysts: Karstedt's catalyst (Pt 2 (dvs) 3 (I), PtO 2 /XPhos (XPhos = 2-dicyclohexylphosphino-2′,4′,6′-tri-(iso-propyl)biphenyl) (II), and Pt(PPh 3 ) 4 (III)) (Table 1, entries 1−6). The reactions were carried out with reagents in a ratio [1]: [2] = 1:3, in toluene or tetrahydrofuran (THF), at 100 °C, without any purification of the acquired chemicals. The progress of the reactions was monitored by 1 H NMR after 24 h, while the process selectivity was calculated using 1 H and 29 Si NMR.…”

“…Trifunctional incompletely condensed silsesquioxanes (RSiMe 2 O) 3 R′ 7 Si 7 O 9 ( IC-POSS s) have attracted much attention since they were first recognized as building nanoblocks for the synthesis of advanced hybrid materials. − These compounds, based on the silicon–oxygen cubic core in which one corner is open, inherit many features of completely condensed polyhedral oligomeric silsesquioxanes (R 8 Si 8 O 12 , POSS) and at the same time possess unique properties that can give them an advantage over the POSS in some areas of application. For instance, it was found that open-cage structures IC-POSS s are characterized by excellent thermal stability, similar to their POSS analogues.…”

UV-Resistant Trifluoropropyl-Substituted Open-Cage Silsesquioxane-Pendant Polysiloxanes

“…The syntheses of 3,7,14-tris(dimethylsilylsiloxy)hepta(3,3,3trifluoropropyl)tricycloheptasiloxane (TFP-H) and 3,7,14-tris-( d i m e t h y l v i n y l s i l y l s i l o x y ) h e p t a ( 3 , 3 , 3 -t r ifl u o r o p r o p y l )tricycloheptasiloxane (TFP-V) were prepared according to a previous report. 43 3,7,14-Tris(dimethylallylsilylsiloxy)hepta(3,3,3trifluoropropyl)tricycloheptasiloxane (TFP-A) was synthesized ac-cording to the method for TFP-V in 72% yield. 1 29 Si-NMR (in CDCl 3 , 80 MHz): δ 9.0, −1.8, −66.2, −68.2, −69.5 ppm.…”