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B(C6F5)3-based Lewis pair-catalyzed acrylate polymerization: Lewis base effects on pairing interactions

Polymer Journal volume 56, pages 145–151 (2024)Cite this article

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Abstract

Acrylate polymerizations catalyzed by Lewis pairs (LP) composed of B(C6F5)3 and various Lewis bases (phosphines, amines, and an N-heterocyclic carbene) in dichloromethane were investigated using two procedures based on different monomer/catalyst addition sequences. In procedure 1, Lewis bases were added to B(C6F5)3-activated n-butyl acrylate (nBA), and the polymerization proceeded quantitatively using all Lewis bases at a wide temperature range (−60 °C to 30 °C). A low nucleophilic Lewis base Et3N also initiated the polymerization even at −60 °C. However, t-butyl acrylate was not polymerized, as LP promoted its conversion into acrylic acid and isobutene. In procedure 2, nBA was added to interacting LPs; the type of Lewis base significantly affected the polymerization results. Specifically, polymerization was not observed when 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and PnBu3 were applied; however, similar to the reaction in procedure 1, PPh3, PtBu3, and 1,4-diazabicyclo[2.2.2]octane (DABCO) initiated nBA polymerization. The pairing interactions between LBs/B(C6F5)3 (PPh3, Et3N, DBU, and DABCO) were investigated using the shift of 19F nuclear magnetic resonance signals, demonstrating that weak interacting LPs efficiently initiated the polymerizations in procedure 2.

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Acknowledgements

This research was partially supported by Grants-in-Aid for Scientific Research (22K05211).

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  1. Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya, Aichi, 466-8555, Japan

    Yuka Naganawa, Kazumasa Mori, Shin-ichi Matsuoka & Masato Suzuki

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  1. Yuka Naganawa
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  2. Kazumasa Mori
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YN: data curation, investigation, visualization, and writing–original draft. KM: initial investigation. SM: conceptualization, funding acquisition, project administration, supervision, writing–original draft, and writing–review and editing. MS: supervision, writing–review and editing.

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Correspondence to Shin-ichi Matsuoka.

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Naganawa, Y., Mori, K., Matsuoka, Si. et al. B(C6F5)3-based Lewis pair-catalyzed acrylate polymerization: Lewis base effects on pairing interactions. Polym J 56, 145–151 (2024). https://doi.org/10.1038/s41428-023-00868-4

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