Synthesis of functionalised porous network silsesquioxane polymers

Abstract

Porous polyhedral silsesquioxane (POSS)-based network polymers are prepared using hydrosilation copolymerisation reactions of a silyl-functionalised POSS molecule with a vinyl-functionalised moiety. Characterisation of these solids show them to possess pore structures in the mesoporous regime, and polymers with longer organic linking groups showing evidence of flexible wall structures. Functionalisation of the polymers is carried out by reaction with triflic acid or sodium hydroxide, followed by incorporation of CpTiCl 3 . EXAFS spectroscopy results are consistent with the titanium being coordinated to the oxygen atoms that make up part of a POSS unit.

Tailor‐Made Hybrid Organic–Inorganic Porous Materials Based on Polyhedral Oligomeric Silsesquioxanes (POSS) by the Step‐Growth Mechanism of Thiol‐Ene “Click” Chemistry

“…[4] Polyhedral oligomeric silsesquioxanes (POSS) have the basic structure (RSiO3 = 2 ) n , (n = 8, 10, 12). These are organic-inScheme 1. a) vinylPOSS (RSiO3 =2 ) n shown for n = 8, 10, 12; b) variety of thiol compounds explored in this study; the nomenclature attributed to the linker is identical to the respective polymer; and c) hybrid polymer 1 prepared with vinylPOSS and linker 1. organic hybrid, cage-like nanostructures (e.g., Scheme 1 a) that, in their chemical diversity, have already been used as building blocks for the generation of porous materials through thermolysis [5] and hydrosylation, [6] as well as other coupling reactions. [7] The preparation of monolithic porous materials involving POSS has often been addressed with amines, [8] and through uncontrolled, free-radical copolymerization with other monomers.…”

Ti-Containing Silsesquioxane Gels with Tunable Porosity: Preparation and Catalytic Activity for the Epoxidation of Cyclooctene by Aqueous Hydrogen Peroxide

“…The desorption of nitrogen from these gels was quite slow, and open hysteresis loops [32] were observed, which suggest the presence of ultramicropores less than 0.5 nm in diameter. Nitrogen adsorption isotherms of porous gels, which are very similar to the isotherms of gels from 1 and 2 [27,29], indicate their porosity in the micro to meso range. Note that the N 2 sorption method can not detect the pores in the cubes [29].…”

“…Morris and coworkers have incorporated Ti species into porous silsesquioxane gels by the post-treatment using CpTiCl 3 (Cp = cyclopentadienyl) [29]. Incorporation of discrete Ti-containing silsesquioxane molecules into these gels through stable chemical bonding is obviously much advantageous, since the local structure around Ti species is expected to be retained even in the gels.…”

Cinnamate‐Functionalized Cage Silsesquioxanes as Photoreactive Nanobuilding Blocks

“…80 % at most when octavinyl SQs reacted with octahydride SQs through hydrosilylation. [29,30] Thermogravimetric analysis (TGA) was applied to evaluate the thermal stability of these cinnamate SQ monomers.…”