Single step, metal templated synthesis of nanostructured soluble silsesquioxane catalyst supports

Abstract only

Use of system made of peroxocarboxylic-donating substance and metal-modified polyhedral oligosilsesquioxanes under perhydrolysis, as activator for inorganic peroxygen compounds in oxidizing, washing, cleaning or disinfecting solutions

\u3cp\u3eUse of a system made of peroxocarboxylic-donating substance and metal-modified polyhedral oligosilsesquioxanes (I)-(IV) under perhydrolysis conditions, as an activator for inorganic peroxygen compounds in oxidizing-, washing-, cleaning- or disinfecting-solutions, is claimed. Use of a system made of peroxocarboxylic-donating substance and metal-modified polyhedral oligosilsesquioxanes of formulae (I)-(IV) under perhydrolysis conditions, as an activator for inorganic peroxygen compounds in oxidizing-, washing-, cleaning- or disinfecting-solutions, is claimed. M : metal atom comprising Al, Mn, Fe, In, Co, Ni, Ti, V, Ce, W, Mo, Au, Pd, Pt or Cu; L : anionic or neutral ligands; n : 0 or 1-5; A, B1 : -H, -ML n or -SiR1R2R3; R1-R3 : -OH,-COOH, -OR or R; and R : optionally mono- or polysubstituted carboxy-, phosphono-, sulfo-, sulfato- and/or hydroxy-substituted alkyl-, aryl-, alkaryl- or aralkyl- groups having 1-44C that are interrupted by one or more non-adjacent O-atoms in their alkyl chain. An independent claim is included for washing-, cleaning- or disinfecting-agent, comprising peroxocarboxylic-donating compound and metal-modified polyhedral oligosilsesquioxanes (I)-(IV) under perhydrolysis conditions. [Image].\u3c/p\u3

Using a metal-modified polyhedral oligosilsesquioxane (I), (II), (III) or (IV) as an activator for inorganic peroxygen compounds in oxidizing-, washing-, cleaning- or disinfecting solutions

\u3cp\u3eUsing a metal-modified polyhedral oligosilsesquioxane (I), (II), (III) or (IV) as an activator for inorganic peroxygen compounds in oxidizing-, washing-, cleaning- or disinfecting solutions, is claimed. Using a metal-modified polyhedral oligosilsesquioxane of formula (I), (II), (III) or (IV) as an activator for inorganic peroxygen compounds in oxidizing-, washing-, cleaning- or disinfecting solutions, is claimed. M : metal, preferably Mn, Fe, Mo, Au, Cu or Ce; L : anionic or neutral ligand; n : 0 or 1-5; A, B1 : -H, -ML n or SiR1R2R3; R1, R2, R3 : -OH, -COOH, -OR or R; and R : optionally mono- or polysubstituted carboxy-, phosphono-, sulfo-, sulfato- or hydroxy-substituted 1-44C alkyl, 1-44C aryl, 1-44C alkaryl or 1-44C aralkyl, where the alkyl chain is interrupted by at least one non-adjacent O. Independent claims are also included for: (1) using a system made of peroxocarboxylic acid-forming substance under perhydroloysis conditions and (I), (II), (III) or (IV) for enhancing the cleaning performance of detergents and cleaning agents in an aqueous surfactant containing liquor; (2) using a combination of peroxygen compound and (I), (II), (III) or (IV) for bleaching colored stains during washing of textiles, preferably in aqueous surfactant-containing liquor, or in cleaning solutions for hard surfaces, preferably for tableware, for bleaching colored stains, preferably of tea; and (3) a washing-, cleaning- or disinfecting agent comprising (I), (II), (III) or (IV). [Image] [Image].\u3c/p\u3

Process for manufacturing acrylic acid

\u3cp\u3eThe invention pertains to a process for preparing acrylic acid and/or the ester of acrylic acid and lactic acid from a lactic acid oligomer or polymer, comprising the steps of - bringing a reaction mixture comprising the lactic acid oligomer or polymer to reaction conditions to form acrylic acid and/or the ester of acrylic acid and lactic acid, the reacting mixture comprising a halide source selected from a bromide source and/or a chloride source and optionally an acid selected from the group of acids with a pKa of at most 2.0 and compounds which under reaction conditions decompose under the formation of an acid with a pKa of at most 2.0, with the reaction mixture comprising less than 1 wt. % of water, and - keeping the reaction mixture under reaction conditions for a time sufficient to produce acrylic acid and/or the ester of acrylic acid and lactic acid. It has been found that the use of a bromide source and/or a chloride source in combination with the specified acid results in a process which can be operated to obtain a high yield, and is relatively easy to perform.\u3c/p\u3

A method to form a polyurethane material

\u3cp\u3eA method to form a urethane material, the method comprises blending and reacting at least one isocyanate, at least one isocyanate reactive compound and a metallized polyhedral oligomeric silsesquioxane to provide said urethane material, the metallized polyhedral oligomeric silsesquioxane is a dimeric structure with general formula wherein M represents a metal providing a 6-coordinated metal center, x and y being 1, R1O and R2O represent an alkoxide bridging the 6-coordinated metal centers, R3OH and R4OH represent an alcohol ligand and each of R5, to R18 is selected from the group consisting of alkyl-, polyether- and polyester ligands.\u3c/p\u3

Application of POSS nanotechnology for preparation of efficient Ni catalysts for hydrogen production

\u3cp\u3ePOSS (polyhedral oligomeric silsesquioxanes) nanotechnology was applied for preparation of efficient Ni catalysts for hydrogen production through autothermal reforming of methane (ATR of CH\u3csub\u3e4\u3c/sub\u3e). The novel metal-POSS precursor [Nickel (II) ‒ HeptaisobutylPOSS (C\u3csub\u3e4\u3c/sub\u3eH\u3csub\u3e9\u3c/sub\u3e)\u3csub\u3e7\u3c/sub\u3eSi\u3csub\u3e7\u3c/sub\u3eO\u3csub\u3e9\u3c/sub\u3e(OH)O\u3csub\u3e2\u3c/sub\u3eNi] of Ni nanoparticles was introduced into Ce\u3csub\u3e0.5\u3c/sub\u3eZr\u3csub\u3e0.5\u3c/sub\u3eO\u3csub\u3e2\u3c/sub\u3e support with following calcination and reduction stages of activation. The peculiarity of the genesis of Ni/SiO\u3csub\u3e2\u3c/sub\u3e/Ce\u3csub\u3e0.5\u3c/sub\u3eZr\u3csub\u3e0.5\u3c/sub\u3eO\u3csub\u3e2\u3c/sub\u3e nanomaterials and their characteristics versus deposition mode were studied by X-ray fluorescence spectroscopy, thermal analysis, N\u3csub\u3e2\u3c/sub\u3e adsorption, X-ray diffraction, high-resolution transmission electron microscopy and H2 temperature-programmed reduction. The two kinds of supported Ni-containing particles were observed: highly dispersed Ni forms (1‒2 nm) and large Ni-containing particles (up to 50‒100 nm in size). It was demonstrated that the textural, structural, red-ox and, consequently, catalytic properties of ex-Ni-POSS catalysts depend on the deposition mode. The increase of a portion of difficultly reduced Ni\u3csup\u3e2+\u3c/sup\u3e species is found upon application of intermediate calcination during Ni-POSS deposition that has detrimental effect on the activity of catalyst in ATR of CH4. The Ni/SiO\u3csub\u3e2\u3c/sub\u3e/Ce\u3csub\u3e0.5\u3c/sub\u3eZr\u3csub\u3e0.5\u3c/sub\u3eO\u3csub\u3e2\u3c/sub\u3e catalyst prepared by one-step Ni-POSS deposition exhibits the highest H\u3csub\u3e2\u3c/sub\u3e yield ‒ 80% at T = 800 °C.\u3c/p\u3

Enantioselective epoxidation of beta-methylstyrene catalyzed by immobilized Mn(salen) catalysts in different mesoporous silica supports

Mesoporous silica-supported chiral Mn(salen) catalysts were prepared and evaluated in the heterogeneous asymmetric epoxidation of 15-methylstyrene with NaClO as an oxidant. Homogeneous and immobilized Mn(salen) catalysts exhibit similar cis/trans ratios and ee values when trans-substrate is used but different cis/trans ratios and ee values when cis-substrate is used. The production of trans-epoxides is favored in the heterogeneous asymmetric epoxidation of cis-beta-methylstyrene, whereas the production of cis-epoxides is favored in homogeneous reaction. In addition, the cis/trans ratio and ee value of transepoxides produced from cis-beta-methylstyrene change sequentially with changes in support materials, but the ee value of cis-epoxides does not. The textural properties of immobilized Mn(salen) catalysts can be sequentially adjusted by changing pore dimension and channel length, after which the motion restriction and confinement effect in nanochannels of immobilized Mn(salen) catalysts can be adjusted sequentially. Our results reflect that the collapse step of trans-intermediates is considerably affected by the confinement effect. whereas the rotation step of cis-intermediates is greatly influenced by motion restriction. The motion restriction in nanochannels increases the likelihood of rotation for the C-C single bond of cis-intermediates and favors the production of trans-epoxides. (c) 2008 Published by Elsevier Inc

Design of highly efficient catalyst for rational way of direct conversion of methane

\u3cp\u3eEffects of composition and preparation method of MnNaW/SiO\u3csub\u3e2\u3c/sub\u3e and LaSr/CaO catalysts on their physical-chemical properties and performance in oxidative coupling of methane (OCM) have been studied. For MnNaW/SiO\u3csub\u3e2\u3c/sub\u3e catalysts the synthesis method and type of SiO\u3csub\u3e2\u3c/sub\u3e have a significant effect on the texture, while the Na/W ratio determines the phase composition. The variation of preparation method and temperature of catalyst calcination allows regulation of the metal surface concentration and mode of metal distribution across the SiO\u3csub\u3e2\u3c/sub\u3e support. For LaSr/CaO catalysts the synthesis method determines the specific surface area, surface and phase composition. Correlations between catalyst performance, preparation method and state of the catalyst were established. The rational preparation procedure and perspective composition of OCM catalyst have been developed. The 20La/CaO catalysts prepared by citrate sol-gel method were shown to provide ~20% C\u3csub\u3e2\u3c/sub\u3e yield and ~40% methane conversion at 800 ºC.\u3c/p\u3

Polyhedral oligomeric silsesquioxane (poss)-linked ligands

Polyhedral oligomeric silsesquioxanes (POSS) linked ligand of the general formula (I): L [(R1a)n-1(SiO1,5)n R2a ]k [(R1b)n-1SiO1,5)n R2b ]| [(R1C)n-1SiO1,5)n R2c ]m in which (R1a,b,c)n-1(SiO1,5)n is a polyhedral oligomeric silsesquioxanes (POSS) with n = 4, 6, 8,10, 12, 14, 16 or 18 and R1a, R1b,R1c is each independently selected from the group consisting of same or different branched or linear C1-C20 alkyl chains, cyclo alkyl, C1-C20 alkoxy, aryl, aryloxy, heteroaryl and arylalkyl groups, k, l, m is 0 or 1 provided that k+l+m = 1, R2a, R2b, R2c is a spacer that binds the polyhedral oligomeric silsesquioxane (POSS) to the ligand L and ligand L is an uncharged electron donor

Polysilsesquioxane (POSS)-linked imidazole-based carbene and phosphine ligands for transition metal catalysts

\u3cp\u3ePolyhedral oligomeric silsesquioxanes (POSS) linked ligand of the general formula (I) L [(R 1a ) n-1 (SiO 1,5 ) n R 2a ] k [(R 1b ) n-1 SiO 1,5 ) n R 2b ] l [(R 1c ) n-1 SiO 1,5 ) n R 2c ] m (I) in which (R 1a,b,c ) n-1 (SiO 1,5 ) n is a polyhedral oligomeric silsesquioxanes (POSS) with n = 4, 6, 8,10, 12, 14, 16 or 18 and R 1a , R 1b ,R 1c is each independently selected from the group consisting of same or different branched or linear C 1 -C 20 alkyl chains, cyclo alkyl, C 1 -C 20 alkoxy, aryl, aryloxy, heteroaryl and arylalkyl groups, k, I, m is 0 or 1 provided that k+l+m ¥ 1, R 2a , R 2b , R 2c is a spacer that binds the polyhedral oligomeric silsesquioxane (POSS) to the ligand L and ligand L is an uncharged electron donor.\u3c/p\u3