Porous Materials Based on Poly(methylvinylsiloxane) Cross-Linked with 1,3,5,7-Tetramethylcyclotetrasiloxane in High Internal Phase Emulsion as Precursors to Si-C-O and Si-C-O/Pd Ceramics.

Polysiloxane networks were prepared by hydrosilylation of poly(methylvinylsiloxane) (V3 polymer) with 1,3,5,7-tetramethylcyclotetrasiloxane (D4H) at various Si-Vinyl: Si-H groups molar ratios in water-in-oil high internal phase emulsion (HIPE). Curing the emulsions followed by removal of water led to foamed cross-linked polysiloxane systems differing in the cross-linking degrees, as well as residual Si-H and Si-Vinyl group concentrations. Treatment of thus obtained materials in Pd(OAc)2 solution in tetrahydrofuran resulted in the formation of porous palladium/polymer nanocomposites with different Pd contents (1.09-1.70 wt %). Conducted investigations showed that pyrolysis of the studied materials at 1000 °C in argon atmosphere leads to porous Si-C-O and Si-C-O/Pd ceramics containing amorphous carbon and graphitic phases. Thermogravimetric (TG) analysis of the starting cross-linked polymer materials and those containing Pd nanoparticles revealed that the presence of palladium deteriorates thermal stability and decreases ceramic yields of preceramic networks. The extent of this effect depends on polymer cross-linking density in the system.

Poly(methylvinylsiloxane)-Based High Internal Phase Emulsion-Templated Materials (polyHIPEs)-Preparation, Incorporation of Palladium, and Catalytic Properties.

Poly(methylvinylsiloxane) (V3 polymer) obtained by kinetically controlled anionic ring-opening polymerization of 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane was cross-linked with various amounts of 1,3,5,7-tetramethylcyclotetrasiloxane (D4 H) in w/o high internal phase emulsions (HIPEs). PolyHIPEs thus prepared differed in the polymer cross-linking degree, which affected their porous morphology and total porosity. The obtained V3 polymer-based polyHIPEs were applied as matrices for the incorporation of Pd from the Pd(OAc)2 solution in tetrahydrofuran. This process involved the conversion of Si-H groups remaining in the polymer networks and resulted in the formation of crystalline, metallic Pd in the systems. Mean sizes of the generated Pd crystallites were lower in polyHIPEs of higher than in those of lower polymer cross-linking degrees and porosities (∼5 nm vs ∼8 nm, respectively). The Pd-containing polyHIPEs showed activity in catalytic hydrogenation of the triple carbon-carbon bond in phenylacetylene giving the unsaturated product, styrene with a selectivity of ca. 80%. To the best of our knowledge, this is the first work devoted to polysiloxane-based polyHIPEs with dispersed metallic particles.

Preceramic polysiloxane networks obtained by hydrosilylation of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.

Precreamic polysiloxane networks were prepared by hydrosilylation of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (D(4)(Vi)) with a series of linear hydrogensiloxanes as well as with a cyclic hydrogensiloxane, namely 2,4,6,8-tetramethylcyclotetrasiloxane (D(4)(H)) at various hydrogensiloxane/D(4)(Vi) molar ratios in the starting reaction mixture. FTIR spectroscopic measurements conducted during the processes as well as for the reaction products allowed to reveal that the rate of D(4)(Vi) hydrosilylation as well as its efficiency are influenced by the type of hydrogensiloxane used and by the reactants molar ratio. Ceramic yields determined at 1000°C by thermogravimetric analyses were higher for D(4)(Vi)-D(4)(H) than for D(4)(Vi) - linear hydrogensiloxane networks (86-89% vs 65-76%, respectively). Preceramic polysiloxanes prepared as well as the products of their pyrolysis obtained after thermal investigations were monolithic, pore-less materials.