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Stereoselective syntheses and properties of levoglucosenone-containing polymers linked with 1,4-butanedithiol and their application as organogels

Polymer Journal (2025)Cite this article

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Abstract

Owing to the increase in global concern, the replacement of fossil fuel-derived plastics with biomass polymers has attracted the interest of many researchers in both academia and industry. Levoglucosenone (LGO; 1), which is a biomass compound obtained from cellulose in wood or waste paper, has been used as a feedstock for biomass polymers. We recently discovered the stereoselective formation of tricomponent polymers, including LGO fragments, dicarboxylic dihydrazides and aromatic dithiol. In this report, the syntheses and properties of their analogs using aliphatic dithiol instead of aromatic dithiol are reported. The LGO monomer linked with 1,4-butanedithiol was prepared by the addition of K2CO3. Polycondensation of the monomer with several dicarboxylic dihydrazides proceeded to form the corresponding polyhydrazones. All the C-S and C = N bonds were formed stereoselectively. The obtained polymers showed negative optical rotations, which were complementary to those of aromatic analogs. When the polymerization time increased, DMF-insoluble polymers were obtained, which formed organogels with DMF. The degree of swelling varied between 170% and 469% depending on the carbon number of the dicarboxylic dihydrazide. The elongation of the aliphatic carbon chains was assumed to promote intermolecular entanglement, and the resulting polymers were assumed to behave as network polymers despite the linear chains.

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Acknowledgements

This work was supported by a project (JPNP16002) subsidized by the New Energy and Industrial Technology Development Organization (NEDO) [A.T., T.H., and S.K.], JSPS KAKENHI Grant Numbers JP23K23357 [A.T.], JP22H05554 [A.T.], JP24H01304 [A.T.], JSPS LEADER Grant Number JPMXS0320200558 [A.T.] and JST SPRING Grant Number JPMJSP2114 [S.Y.]. The X-ray diffraction study for Compound 3 was conducted by Mr. Taisuke Matsumoto (Kyushu University).

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Authors and Affiliations

  1. Graduate School of Pharmaceutical Sciences, Tohoku University, Miyagi, Japan

    Shogo Yashiro, Honoka Ishikawa, Takayuki Doi & Atsushi Tahara

  2. Frontier Research Institute for interdisciplinary Sciences (FRIS), Tohoku University, Miyagi, Japan

    Honoka Ishikawa, Takashi Itoh & Atsushi Tahara

  3. Seiko PMC Corporation, Tokyo, Japan

    Toshio Hokajo

  4. Graduate School in Complex Systems Chemistry, University of Strasbourg, Strasbourg, France

    Kerem Bolukbasi

  5. Institute for Materials Chemistry and Engineering (IMCE), Kyushu University, Fukuoka, Japan

    Shinji Kudo

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  1. Shogo Yashiro
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Correspondence to Atsushi Tahara.

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Yashiro, S., Ishikawa, H., Hokajo, T. et al. Stereoselective syntheses and properties of levoglucosenone-containing polymers linked with 1,4-butanedithiol and their application as organogels. Polym J (2025). https://doi.org/10.1038/s41428-025-01088-8

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