Volume 2021, Issue 19 p. 1836-1845
Full Paper

Interlayer Silylation of Layered Octosilicate with Organoalkoxysilanes: Effects of Tetrabutylammonium Fluoride as a Catalyst and the Functional Groups of Silanes

Masashi Yatomi

Masashi Yatomi

Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo, 169-8555 Japan

These authors contributed to this work equally.

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Dr. Masakazu Koike

Dr. Masakazu Koike

Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo, 169-8555 Japan

These authors contributed to this work equally.

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Dr. Nadège Rey

Dr. Nadège Rey

Univ Montpellier, CNRS, ENSCM, 8 rue de l'école normale, 34290 Montpellier Cedex 5, France

Sorbonne Université, CNRS, Collège de France Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), 4 place Jussieu, 75005 Paris, France

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Yuki Murakami

Yuki Murakami

Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo, 169-8555 Japan

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Dr. Shohei Saito

Dr. Shohei Saito

Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo, 169-8555 Japan

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Prof. Dr. Hiroaki Wada

Prof. Dr. Hiroaki Wada

Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo, 169-8555 Japan

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Prof. Dr. Atsushi Shimojima

Prof. Dr. Atsushi Shimojima

Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo, 169-8555 Japan

Kagami Memorial Research Institute for Materials Science and Technology, Waseda University, 2-8-26 Nishiwaseda, Shinjuku-ku, Tokyo, 169-0051 Japan

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Dr. David Portehault

Dr. David Portehault

Sorbonne Université, CNRS, Collège de France Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), 4 place Jussieu, 75005 Paris, France

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Dr. Sophie Carenco

Dr. Sophie Carenco

Sorbonne Université, CNRS, Collège de France Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), 4 place Jussieu, 75005 Paris, France

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Prof. Dr. Clément Sanchez

Prof. Dr. Clément Sanchez

Sorbonne Université, CNRS, Collège de France Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), 4 place Jussieu, 75005 Paris, France

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Dr. Carole Carcel

Dr. Carole Carcel

Univ Montpellier, CNRS, ENSCM, 8 rue de l'école normale, 34290 Montpellier Cedex 5, France

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Dr. Michel Wong Chi Man

Corresponding Author

Dr. Michel Wong Chi Man

Univ Montpellier, CNRS, ENSCM, 8 rue de l'école normale, 34290 Montpellier Cedex 5, France

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Prof. Dr. Kazuyuki Kuroda

Corresponding Author

Prof. Dr. Kazuyuki Kuroda

Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo, 169-8555 Japan

Kagami Memorial Research Institute for Materials Science and Technology, Waseda University, 2-8-26 Nishiwaseda, Shinjuku-ku, Tokyo, 169-0051 Japan

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First published: 04 April 2021
Citations: 1

Graphical Abstract

Interlayer silylation of layered octosilicate with organotriethoxysilane was enhanced by the addition of TBAF. The F in TBAF attacks the silicon in alkoxysilanes, which increases the reactivity with SiOH groups on the layer surface. The effect of F on silylation depends on the kind of functional organic group of organotriethoxysilanes, because the interlayer accessibility is varied with functional groups.

Abstract

Interlayer silylation of layered sodium octosilicate (Na-Oct) with various organoalkoxysilanes was conducted using hexadecyltrimethylammonium ion-exchanged layered octosilicate (C16TMA-Oct) as an intermediate in the presence or absence of tetrabutylammonium fluoride (TBAF). The degree of silylation was increased by adding TBAF. It is suggested that F ions perform a nucleophilic attack on the alkoxysilanes, which promotes the silylation reaction. C16TMA-Oct was silylated with octyltriethoxysilane (C8TES) or 3-mercaptopropyltriethoxysilane (MPTES) to compare the reactivity of the two organoalkoxysilanes in the presence or absence of TBAF. A higher degree of silylation of C16TMA-Oct was observed with MPTES, suggesting the higher accessibility of this silylating agent into the interlayer polar region of C16TMA-Oct. Overall TBAF appears as a relevant catalyst for the covalent interlayer surface modification of layered silicates with organic functional groups.

Conflict of interest

The authors declare no conflict of interest.