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Preparation and characterization of two-dimensional sheet-shaped poly(methyl methacrylate) synthesized via γ-ray polymerization in nanoclay template

Polymer Journal volume 55, pages 957–965 (2023)Cite this article

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Abstract

Two-dimensional sheet-shaped poly(methyl methacrylate) (2d-PMMA) with crosslinking only in the two-dimensional direction was synthesized via planar polymerization of MMA monomer in montmorillonite (MMT) nanolayers by using γ-ray irradiation, and the samples obtained were characterized. Size-exclusion chromatography with a multi-angle light scattering (SEC-MALS) measurements of the obtained sample showed bimodal peaks: a main peak with a longer elution time and an apparent molecular weight Mw,app and radius of gyration Rg in tetrahydrofuran (THF) similar to those for linear PMMA samples, and a subpeak with a shorter elution time and Mw,app and Rg evidently lower than those for the linear PMMA samples. This result indicated that polymers with moderate branching and crosslinking were contained in the subpeak. Atomic force microscopy (AFM) observation of the sample showed the presence of sheet-shaped molecules with a height of ca. 0.6 nm, corresponding to the thickness of one MMA monomer, and a width of several to several tens of nanometers, showing a broad distribution in molecular width. The subpeak portion was isolated via SEC fractionation, and its AFM observation showed thin circular disk-shaped molecules with relatively uniform size (i.e., a width of several tens of nanometers). However, in these molecules, two types of molecular heights (i.e., 0.6 and 1.2 nm) were identified. This result indicated that MMA monomers were filled as two layers within one MMT interlayer, and the polymerization reaction proceeded in that state. The similarity in the molecular size of 2d-PMMA observed via AFM and SEC-MALS was confirmed. These results demonstrated that the desired sheet-shaped polymers were obtained through the above synthesis and fractionation process.

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Acknowledgements

The authors would like to acknowledge Mr. Shigefumi Imai and Dr. Jun Kumagai at Nagoya University for γ-ray irradiation experiments. The authors would also like to acknowledge Dr. Nobuhiko Hosono at The University of Tokyo for his fruitful discussion. This work was partly supported by the Iketani Science and Technology Foundation, Shimadzu Science Foundation, the Leave a Nest Grant Toyobo Polymer Science award, and YD would like to acknowledge these funding agencies.

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  1. Department of Materials Physics, Nagoya University, Nagoya, 4648603, Japan

    Yuya Doi, Takato Ishida, Takashi Uneyama & Yuichi Masubuchi

  2. Department of Molecular and Macromolecular Chemistry, Nagoya University, Nagoya, 4648603, Japan

    Mitsuo Hara, Takahiro Seki & Atsushi Takano

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Correspondence to Yuya Doi.

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Doi, Y., Hara, M., Seki, T. et al. Preparation and characterization of two-dimensional sheet-shaped poly(methyl methacrylate) synthesized via γ-ray polymerization in nanoclay template. Polym J 55, 957–965 (2023). https://doi.org/10.1038/s41428-023-00795-4

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