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Facile synthesis of amine-substituted cyclosiloxanes via a photocatalytic thiol-ene reaction to generate ketoenamine-linked hybrid networks

Polymer Journal volume 54, pages 1257–1265 (2022)Cite this article

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Abstract

Multiarmed functional cyclosiloxanes were obtained via a facile synthesis through the photocatalytic thiol-ene reaction of 1,3,5-trivinyl-1,3,5-trimethylcyclosiloxane (D3V), 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclosiloxane (D4V), and 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane (D5V) with cysteamine hydrochloride under mild conditions. A subsequent desalting reaction with triethylamine was conducted to obtain amine-functionalized cyclosiloxanes with ring structures (D4A and D5A). The chemical structures were confirmed by nuclear magnetic resonance, Fourier transform infrared spectroscopy, and matrix-assisted laser desorption ionization time-of-flight mass spectra. The regioselectivities of the final products were determined with β-adducts as high as 93% irrespective of the number of cyclosiloxane rings. The amino-functionalized cyclosiloxane monomers underwent a mild Schiff base reaction to obtain hybrid networks. Their morphologies, thermal properties, and porosities were also investigated.

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Acknowledgements

HZ appreciates financial support from the Toyo Suisan Foundation. MM thanks Toshiaki Ogasawara Memorial Foundation for financial support. The authors are also grateful to Prof. Hirotomo Nishihara (Tohoku University) for his kind support with the nitrogen adsorption tests.

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Authors and Affiliations

  1. Graduate School of Engineering, Tohoku University, 6-6-11 Aramaki Aza Aoba, Aoba-ku, Sendai, 980-8579, Japan

    Huie Zhu, Yuhi Watanabe, Naoki Yoshida, Yuya Ishizaki & Masaya Mitsuishi

  2. Advanced Institute for Materials Research (AIMR), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577, Japan

    Mao Ohwada & Rui Tang

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  1. Huie Zhu
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Zhu, H., Watanabe, Y., Yoshida, N. et al. Facile synthesis of amine-substituted cyclosiloxanes via a photocatalytic thiol-ene reaction to generate ketoenamine-linked hybrid networks. Polym J 54, 1257–1265 (2022). https://doi.org/10.1038/s41428-022-00678-0

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