Polyfunctional cubic silsesquioxanes as building blocks for organic/inorganic hybrids

Abstract

Cubic silsesquioxanes, [RSiO 1.5 ] x , potentially offer access to organic/inorganic hybrids wherein the exact shape, size and mechanical properties of the inorganic component are perfectly defined. Furthermore, by tailoring the organic functionality bound to silicon, the inorganic/ organic interface can also be perfectly defined. Finally, careful selection of the polymerizable groups in the organic moieties can provide goodto-excellent control of the crosslinked density or degree of polymerization of the resulting hybrid materials. Thus, cubic silsesquioxanes may be exceptional model materials for inorganic/organic hybrids. Methods of synthesizing cubes with liquid-crystalline and/or polymerizable organic moieties are described. Some thermal properties are discussed. The catalytic copolymerization of the octavinyldimethylsiloxy-functionalized cube with the octahydridodimethylsiloxy-functionalized cube to produce a material with well-defined microporosity and high surface area is described.

Tailored Synthesis and Fundamental Characterization of Organic‐Inorganic Hybrid Gels by Means of a Hydrosilylation Reaction

“…Various methods have been proposed and investigated for preparing organic-inorganic hybrid materials, for example, nanocomposites, the sol-gel technique, interpenetrating polymer networks and so on. [1][2][3][4][5][6][7][8][9][10] Among hybrid materials, organic-inorganic polymeric materials containing Si atoms, such as polysiloxanes, have been the most studied and are widely used due to their characteristic properties of thermal and oxidative stability and optical transparency. [11][12][13] Furthermore, not only linear polymers but also network polymers have been developed as organicinorganic polymers.…”

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Organic-inorganic hybrid gels have been synthesized from siloxane, 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS), tetrakis(dimethylsilyloxy)silane (TDSS) or silsesquioxane, 1,3,5,7,9,11,13,15-octakis(dimethylsilyloxy)-pentacyclo-[9,5,1,1,1,1]octasilsesquioxane (POSS), as crosslinking reagents and a,o-nonconjugated dienes, 1,5-hexadiene (HD), 1,7-octadiene (OD) and 1,9-decadiene (DD), using a hydrosilylation reaction with a Pt catalyst. The network structures of the resulting gels were investigated by means of a novel scanning microscopic light scattering system.

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Synthesis and Structure of Organic-Inorganic Hybrid Semi-interpenetrating Polymer Network Gels

“…The organic-inorganic hybrid polymers have been prepared by some effective methods (Mark et al, 1995;Mascia, 1995;Novak, 1993;Provatas et al, 1997;Laine et al, 1998;Vaia et al, 1996;Sogah et al, 1999;Saegusa et al, 1991;Landry st al., 1993;Yamada et al, 1997;Chujo et al, 2003;Laine et al, 2003;Galiastsatos et al, 2001). Hydrosilylation reaction of multi-functionalized crosslinking reagents containing Si-H or vinyl group is one of the effective methods to yield the organic-inorganic network polymers containing Si (Yoshida et al, 2004(Yoshida et al, , 2001Tsumura et al, 1998Tsumura et al, , 1999Michalczyk et al, 1993;Lercher et al, 2002;Laine et al, 1998;Schaefer et al, 2003). The authors recently attained effective synthesis of organic-inorganic hybrid gels by means of a hydrosilylation reaction of cyclic siloxane or cubic silsesquioxane with ,-nonconjugated dienes.…”

Preparation of Ionic Polysilsesquioxanes with Regular Structures and Their Ion-Exchange Behaviors

“…However, even though various kinds of polyhedral oligomeric SQs (POSS) are known as SQs with controlled molecular structures (Scheme 1b) (Feher & Wyndham, 1998;Laine et al, 1998;Zhang et al, 2007;Cordes et al, 2010;Tanaka et al, 2010;Tanaka & Chujo, 2012), the regularly structured polySQs (PSQs) have only been obtained in the limited cases. This is because PSQs are prepared by polycondensation of the trifunctional silane monomers such as organotrialkoxysilanes and organotrichlorosilanes.…”