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Synthesis and crystallization-induced microphase separation of cellulose triacetate-block-poly(γ-benzyl-l-glutamate)

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Abstract

This article describes the first observation of crystallization-induced microphase separation in thin film and bulk cellulose triacetate-block-poly(γ-benzyl-l-glutamate) (PBLG) [cellulose triacetate (CTA)-b-PBLG] via copper-catalyzed azide–alkyne cycloaddition (CuAAC) between azido-functionalized CTA at the reducing end and alkyne-functionalized PBLG at the C-terminus. The reactivity of the amino group at the C-1 position of the glucosyl residue at the reducing end for the initiation reaction of the ring-opening polymerization (ROP) of γ-benzyl-l-glutamate N-carboxyanhydride was compared to that of the azido group at the reducing end of CTA for CuAAC, with PBLG bearing an alkyne group at the C-terminus. Although the amino group at the reducing end of CTA exhibited no reactivity as a macroinitiator for ROP of BLG, the azido group at the reducing end of CTA reacted with the alkyne group at the C-terminus of PBLG to afford CTA-b-PBLG. The structure of CTA-b-PBLG was characterized by 1H- and 13C-nuclear magnetic resonance spectroscopies, infrared spectroscopy, differential scanning calorimetry, and wide angle X-ray diffractometry. Microphase separation of the film and bulk of CTA-b-PBLG was clearly shown by atomic force microscopy, field-emission scanning electron microscopy, and transmission electron microscopy.

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Acknowledgments

We are indebted to Prof. Yoshiyuki Nishio of Kyoto University for the discussion on thermal analysis. We thank the Japan Society for the Promotion of Science (JSPS) for their financial support of this study, in part, through Grant-in-Aid for Scientific Research (nos. 21580205 and 24380092), and a Sekisui Chemical Grant Program for Research.

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  1. Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan

    Hiroshi Kamitakahara, Akihiro Baba, Arata Yoshinaga, Ryo Suhara & Toshiyuki Takano

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  1. Hiroshi Kamitakahara
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  2. Akihiro Baba
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  3. Arata Yoshinaga
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Correspondence to Hiroshi Kamitakahara.

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Kamitakahara, H., Baba, A., Yoshinaga, A. et al. Synthesis and crystallization-induced microphase separation of cellulose triacetate-block-poly(γ-benzyl-l-glutamate). Cellulose 21, 3323–3338 (2014). https://doi.org/10.1007/s10570-014-0383-3

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