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POSS cage-scrambling-induced gelation of POSS-pendant random copolymers catalyzed by fluoride anions

Polymer Journal volume 53, pages 1213–1222 (2021)Cite this article

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Abstract

Polyhedral oligomeric silsesquioxane (POSS) is a versatile building block for various organic/inorganic hybrid materials. However, its intrinsic reactivity has attracted limited attention, particularly in polymer chemistry. This study investigated the cage-scrambling properties of POSS-pendant random copolymers catalyzed by fluoride anions, leading to gelation of a solution of random copolymers. A series of POSS-pendant random copolymers was prepared using POSS-containing methacrylates and several vinyl monomers. The gelation properties were first investigated in detail using P(PhPOSSMA-r-BMA) by varying the POSS content and reaction conditions. The insoluble product was characterized by FT-IR and solid-state 29Si-NMR, the results of which support the intermolecular cage-scrambling reaction of the pendant POSS moieties via transient siloxane cleavage. Chloride and bromide anions also acted as catalysts for the scrambling reaction. Altering the comonomer or the vertex substituents resulted in varying gelation times depending on each structural characteristic. The unique polymer reaction presented herein opens up a wider range of uses for POSS—not only as an inorganic component but also as an intrinsically reactive moiety in various organic/inorganic hybrid polymer materials.

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Acknowledgements

This study was financially supported by the Ministry of Education, Culture, Sports, Science, and Technology-Supported Program for the Strategic Research Foundation at Private Universities (No. S1311032), 2013–2017.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, Kanagawa, 221-8686, Japan

    Akira Takahashi, Tatsumi Okada, Keiichiro Nakano & Atsushi Kameyama

  2. Center for Fundamental Education, Teikyo University of Science, 2525 Yatsusawa, Uenohara, Yamanashi, 409-0133, Japan

    Yoshihito Ishida

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Correspondence to Akira Takahashi or Atsushi Kameyama.

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Takahashi, A., Okada, T., Nakano, K. et al. POSS cage-scrambling-induced gelation of POSS-pendant random copolymers catalyzed by fluoride anions. Polym J 53, 1213–1222 (2021). https://doi.org/10.1038/s41428-021-00523-w

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