Synthesis of ion-exchangeable layered polysiloxane by sol–gel reaction of aminoalkyltrialkoxysilane: a new preparation method for layered polysiloxane materials

Kaneko, Yoshirō; Iyi, Nobuo; Matsumoto, Taki; Fujii, Kazuko; Kurashima, Keiji; Fujita, Taketoshi

doi:10.1039/b305545k

Cited by 69 publications

(71 citation statements)

References 23 publications

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“…An alternative to prepare easy handling materials is the crystallization in acetone or the lyophilization process, in dry conditions. 22,23 Even so, the material does not seem to have mechanical resistance to manipulation in open ambient condition. In the present work, to overcome this difficulty and to increase the possibility of applications for this kind of materials as stable two dimensional nanospaces for chemical processes, [24][25][26][27][28] we have obtained a sample series of hybrid layered materials with the cationic ammoniumpropyl group and containing different amounts of inorganic component to improve the handling possibilities.…”

Section: Introductionmentioning

confidence: 99%

“…[18][19][20][21] More recently, it was reported that layered structures in silsesquioxanes containing charged pendant organic groups can be prepared using aminopropyltrimethoxysilane as precursor reagent, in very acid medium. 22,23 The resulting product is a water soluble and viscous liquid of difficult handling. An alternative to prepare easy handling materials is the crystallization in acetone or the lyophilization process, in dry conditions.…”

Section: Introductionmentioning

confidence: 99%

“…738 medium. 22,23 The resulting product is a water soluble and viscous liquid of difficult handling. An alternative to prepare easy handling materials is the crystallization in acetone or the lyophilization process, in dry conditions.…”

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confidence: 99%

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An innovative series of layered nanostructured aminoalkylsilica hybrid material

Trindade

Stoll

Pereira

et al. 2009

J. Braz. Chem. Soc.

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Uma nova série de amostras de material híbrido à base de sílica, contendo o grupo catiônico amoniopropil ligado na forma pendente, foi obtida usando-se o método sol-gel de síntese, variandose a razão molar entre o precursor inorgânico e o precursor orgânico. A análise termogravimétrica mostrou que as amostras são termicamente estáveis até 260 °C. Os resultados obtidos por difratometria de raios X, microscopia eletrônica de transmissão, ressonância magnética nuclear de 29 Si e análise elementar são compatíveis com o modelo estrutural de camadas de silsesquioxano com distâncias basais de até 5,4 nm, contendo sílica amorfa no espaço entre as camadas.An innovative series of silica-based hybrid materials containing pendant cationic ammoniumpropyl groups was obtained using the sol-gel method, by varying the molar ratio of the inorganic and organic precursors. Thermogravimetric analysis showed that samples were thermally stable up to 260 °C. Results obtained by X-ray diffractometry, transmission electron microscopy, 29 Si nuclear magnetic resonance and elemental analysis were compatible with a silsesquioxane layered structural model showing basal distances up to 5.4 nm, containing amorphous silica in the interlayer space. Keywords: nanostructured materials, layered hybrid materials, silsesquioxanes IntroductionThe development of organic-inorganic silica-based hybrid materials has received growing attention in the last decades. These materials present characteristics of the individual components as well as new unexpected properties.1-6 A satisfactory method to obtain these hybrid materials is the sol-gel synthesis, which allows dispersion of the components in nano or molecular scale, combining their physicochemical properties or producing new ones. Among this ensemble, the self-organized silica-based hybrid materials are very promising, because a great quantity of novel materials with attractive properties can be obtained. [7][8][9][10][11][12] They can be prepared using proper organosilane precursors presenting two or more polycondensation points, which are gelified together with an inorganic alkylorthosilicate precursor. The self-organization of these hybrid materials is imposed by the rigidity of the organic groups chemically bonded in a bridged way to the inorganic moiety. [11][12][13][14][15] In recent times it was demonstrated that self-organized materials can also be obtained using bridging charged organic groups. 16,17 It is important to point out that the selforganization in silica-based hybrid material has always been associated with the presence of bridging organic groups. Up to the present time, as far as we know, the synthesis of self-organized silica-based hybrid materials containing pendant organic groups has not been reported.Another kind of hybrid materials can be obtained by gelation of organosilanes without addition of alkylorthosilicate inorganic precursors. These materials, called silsesquioxanes, have elevated organic content and can also present self-organization properties. Among them, the polyhe...

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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An innovative series of layered nanostructured aminoalkylsilica hybrid material

Trindade

Stoll

Pereira

et al. 2009

J. Braz. Chem. Soc.

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“…As estruturas para silsesquixanos que têm sido relacionadas na literatura são estruturas: i) aleatória, onde os oligômeros não mostram arranjos ordenados (Figura 9a); ii) bidimensional, que podem ter arranjo em camadas 66,67 ou na forma de escada; 68,69 (Figura 9b); iii) tridimensionais, conhecidos por POSS Polyhedral Oligomeric Silsesquioxanes [68][69][70] (Figura 9c). Na Figura 9 estão representadas essas estruturas.…”

Section: Silsesquioxanosunclassified

Materiais híbridos à base de sílica obtidos pelo método sol-gel

Benvenutti¹,

Moro²,

Costa³

et al. 2009

Quím. Nova

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Recebido em 16/12/08; aceito em 16/3/09; publicado na web em 17/9/09 SILICA BASED HYBRID MATERIALS OBTAINED BY THE SOL-GEL METHOD. This review deals with silica based hybrid materials obtained by the sol-gel method. It involves concepts, classifications and important definitions regarding the sol-gel method that allows obtaining materials with organic and inorganic components dispersed in a molecular or nanometric level. We discuss the properties and characteristics of hybrid materials related to experimental synthesis conditions. We devote a special attention to the nanostructured materials, where the self-organization is imposed by the organic component. Finally, we present some important applications of these materials based on their specific properties.Keywords: organic-inorganic materials; silsesquioxanes; silica based hybrid xerogels. INTRODUÇÃOO desenvolvimento da ciência dos materiais trouxe importantes contribuições no avanço da tecnologia. A busca constante por novos materiais com desempenho e propriedades otimizadas para aplicações inovadoras e o aperfeiçoamento de materiais já existentes é um desafio e um dos motivos da evolução técnica e científica atual.1-8 Nesse contexto, encontra-se a possibilidade de combinar no nível molecular ou nanométrico os componentes orgânico e inorgânico, resultando em novos materiais conhecidos como híbridos organo-inorgânicos.9 Esses materiais híbridos, além de oferecerem a oportunidade de combinar de forma sinérgica as propriedades físico-químicas inerentes de seus constituintes, permitem obter novas propriedades, resultantes da combinação de seus componentes, devido ao tamanho reduzido dos domínios que os compõem.10-13 Para alcançar esse nível tão reduzido de dispersão, pode-se utilizar o método sol-gel de síntese, que envolve a formação de uma rede polimérica inorgânica por reações de gelificação a baixas temperaturas. As reações resultam na transição de um líquido para um sólido, sendo que os reagentes precursores dos componentes, orgânico e inorgânico, que são geralmente alcóxidos de silício ou de metais como alumínio, titânio, zircônio, se encontram inicialmente dissolvidos nesse líquido. No decorrer do processo, as reações de gelificação levam à formação de um estado sol, que se caracteriza por apresentar oligômeros que formarão cadeias de dimensões coloidais e partículas primárias dispersas. A evolução desse processo forma o estado gel que apresenta conectividade entre as unidades de dimensões coloidais, formando uma rede tridimensional, entrelaçada macroscopicamente observável.14 Além da possibilidade de obter os componentes orgânico e inorgâ-nico altamente dispersos, o método sol-gel de síntese apresenta outras características interessantes, tais como: i) as reações de gelificação são processadas a baixas temperaturas, o que permite inserir à matriz sólida biomoléculas como enzimas, proteínas e anticorpos, de difícil incorporação por outros métodos que utilizem temperaturas mais elevadas;15-17 ii) possibilidade de obter materiais sob diferentes configurações ...

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“…Poly(aminopropylsilsesquioxane) (PASQ) from the hydrolytic condensation of APS has been developed rapidly as a precursor to organic/inorganic hybrid polymers, 3 as starting material of a two-dimensional polysiloxane complex 4 and as a core for starburst dendrimers due to reactive amino groups, 5 but it is highly hygroscopic. Many properties of polylsilsesquioxanes can be modified by combining two or more RSiO 3=2 components (R is hydrogen or any alkyl, alkylene, aryl, arylene, or their organo-functional derivatives).…”

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confidence: 99%

Hydrolytic Co-condensation of Phenyltriethoxysilane with γ-Aminopropyltriethoxysilane in the Presence of Sodium Dodecyl Sulfate

Liu

Zhou

et al. 2006

Polym J

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ABSTRACT:The hydrolytic co-condensation of hydrophobic phenyltriethoxysilane (PTES) and hydrophilicaminopropyltriethoxysilane (APS) under basic catalysis in the presence of sodium dodecyl sulfate (SDS) was investigated. Copolymer particles were influenced significantly by APS/PTES molar ratios, total monomer and SDS concentration. Amino group content of the copolymer was determined by element analysis and back titration. Scanning electron micrographs revealed the morphologies of the copolymer particles. FT-IR, solid state 29 Si NMR and TGA were used to characterize the copolymer. [DOI 10.1295/polymj.38.220] KEY WORDS -Aminopropyltriethoxysilane / Phenyltriethoxysilane / Sodium Dodecyl Sulfate / Hydrolytic Co-condensation / Copolymer Particles / Poly(phenylsilsesquioxane) (PPSQ) from the hydrolytic condensation of phenyltriethoxysilane exhibits outstanding thermal stability, good solubility in common organic solvents and fine electric insulting properties, 1,2 but its compatibility and reactivity with other polymers are not good enough. Poly(aminopropylsilsesquioxane) (PASQ) from the hydrolytic condensation of APS has been developed rapidly as a precursor to organic/inorganic hybrid polymers, 3 as starting material of a two-dimensional polysiloxane complex 4 and as a core for starburst dendrimers due to reactive amino groups, 5 but it is highly hygroscopic. Many properties of polylsilsesquioxanes can be modified by combining two or more RSiO 3=2 components (R is hydrogen or any alkyl, alkylene, aryl, arylene, or their organo-functional derivatives).6,7 The co-condensation method enables better control of the density of functional groups, then control of properties. It is expected that the co-condensation of PTES and APS will yield novel functional silsesquioxanes and the hybrid silsesquioxane will combine the advantages of PPSQ with APSQ. Tunney's patent claimed the preparation of such a poly(aminopropyl/phenylsilsesquioxane) (PAPSQ) by the hydrolytic co-condensation and its use as a precursor of organic/inorganic hybrid materials by imidization or amidation, 8 but no experimental details or characterization data were supplied. Their scheme under acid catalyst employs expensive tetrahydrofuran (THF) as co-solvent and isolation and purification is complicated. PAPSQ has been investigated in a Stöber-like method in our laboratory, 9 but some shortcomings such as low amino group contents and large particle diameter are insuperable from the method. This paper presents a useful alternative for the control of particle size and amino content of the copolymer, and provides easy access to a polysilsesquioxane copolymer with a relatively high degree of functionality. Anionic surfactant SDS was used, which has been shown effective in controlling the size of poly(phenylsilsesquioxane) 10 and poly(phenyl/methylsilsesquioxane) particles.11 Spheroidal copolymer particles with high amino group content are prepared by the hydrolytic co-condensation of hydrophobic PTES and hydrophilic APS in the presence of SDS. Knowledge of the...

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Synthesis of ion-exchangeable layered polysiloxane by sol–gel reaction of aminoalkyltrialkoxysilane: a new preparation method for layered polysiloxane materials

Cited by 69 publications

References 23 publications

An innovative series of layered nanostructured aminoalkylsilica hybrid material

An innovative series of layered nanostructured aminoalkylsilica hybrid material

Materiais híbridos à base de sílica obtidos pelo método sol-gel

Hydrolytic Co-condensation of Phenyltriethoxysilane with γ-Aminopropyltriethoxysilane in the Presence of Sodium Dodecyl Sulfate

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