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Changes in amorphous structure and reaction acceleration during bulk polymerization of methacrylates

Polymer Journal volume 56, pages 1005–1015 (2024)Cite this article

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Abstract

It has long been known that a sudden reaction acceleration (i.e., the Trommsdorff effect) occurs during bulk polymerization of methacrylates. While this effect has been qualitatively explained by an increased macroscopic viscosity and decreased termination rate, the detailed mechanism is still debated. This is because the effect occurs so suddenly that the change in macroscopic viscosity is not sufficient to explain the effect quantitatively. Less attention has been given to the change in the amorphous structure during bulk polymerization. In this study, we investigate the amorphous structure during bulk polymerization of methyl methacrylate (MMA), ethyl methacrylate (EMA), and butyl methacrylate (BMA) via X-ray scattering. The amorphous structure changes dramatically at some point during bulk polymerization. To obtain detailed microscopic information, we applied pair distribution function (PDF) analysis during the bulk polymerization of MMA. Our results suggest that a change in the amorphous structure influences the reaction kinetics during bulk polymerization.

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Acknowledgements

Y.S. acknowledges financial support by JSPS KAKENHI grant no 22K14015. The synchrotron radiation experiments were performed with the BL40B2 and BL08W beamlines at SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI). The proposal numbers are 2021B1338, 2022A1220, and 2023A1189. The authors acknowledge experimental support from Dr. Noboru Ohta and Dr. Hiroshi Sekiguchi from BL40B2, as well as Dr. Hiroki Yamada, and Dr. Seiya Shimono from BL08W.

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Authors and Affiliations

  1. Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka, Japan

    Yasuhito Suzuki, Ryutaro Mishima & Akikazu Matsumoto

  2. Department of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka, Japan

    Yasuhito Suzuki, Shodai Onozato & Akikazu Matsumoto

  3. Diffraction and Scattering Division, Center for Synchrotron Radiation Research, Japan Synchrotron Radiation Research Institute, Hyogo, Japan

    Jo-chi Tseng

  4. Faculty of Materials for Energy, Shimane University, 1060, Nishi-Kawatsu-Cho, Matsue, Shimane, Japan

    Satoshi Hiroi, Kentaro Kobayashi & Koji Ohara

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  1. Yasuhito Suzuki
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  2. Ryutaro Mishima
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Correspondence to Yasuhito Suzuki.

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Suzuki, Y., Mishima, R., Onozato, S. et al. Changes in amorphous structure and reaction acceleration during bulk polymerization of methacrylates. Polym J 56, 1005–1015 (2024). https://doi.org/10.1038/s41428-024-00943-4

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