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Synthesis of methylcellulose model copolymers with heterogeneous distribution and their solution properties

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Abstract

In order to elucidate the characteristic features of commercial methylcellulose precisely, O-methylcellulose model copolymers consisting of 2,3,6-tri-O-methylanhydroglucose unit (236MeAGU) and 2-O-methylanhydroglucose unit (2MeAGU) with various composition ratios were synthesized via cationic ring-opening copolymerization of the corresponding glucose orthoester derivatives, subsequent removal of pivaloyl and allyl groups, and methylation. The structure of the obtained copolymers was confirmed by 1H-, 13C-NMR, and FT-IR. Temperature-dependent turbidity measurement verified their thermoresponsive behavior in aqueous solution. The lower critical solution temperature was tuned from 63 to 45 °C above 47 mol-% 236MeAGU content. The hydrophobicity along the cellulose chain was dominant to determine their physical properties. However, the aqueous properties of the MC model copolymers were strongly affected by the slight difference of the composition ratio. The present method would provide further details of the structure–property relationship of O-methylcellulose.

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Abbreviations

AGU:

Anhydroglucose unit

DP:

Degree of polymerization

DS:

Degree of substitution

GPC:

Gel permeation chromatography

LCST:

Lower critical solution temperature

MC:

O-methylcellulose

2MeAGU:

2-O-methylanhydroglucose unit

236MeAGU:

2,3,6-tri-O-methylanhydroglucose unit

M n :

Number-averaged molecular weight

M w :

Weight-averaged molecular weight

2Piv36AllAGU:

3,6-di-O-allyl-2-O-pivaloylanhydroglucose unit

2Piv36MeAGU:

3,6-di-O-methyl-2-O-pivaloylanhydroglucose unit

T CP :

Cloud point on heating

T RCP :

Cloud point on cooling

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Acknowledgments

This investigation was supported in part by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, and Culture of Japan (no. 17380107). K.S. acknowledges the Research Fellowships of the Japan Society for the Promotion of Science (JSPS) for Young Scientists.

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Author notes

  1. Keita Sakakibara

    Present address: World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, Ibaraki, 305-0044, Japan

  2. Fumiaki Nakatsubo

    Present address: Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan

Authors and Affiliations

  1. Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Kyoto, 606-8502, Japan

    Keita Sakakibara, Toshiyuki Takano & Fumiaki Nakatsubo

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  1. Keita Sakakibara
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  2. Toshiyuki Takano
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Correspondence to Toshiyuki Takano.

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Sakakibara, K., Takano, T. & Nakatsubo, F. Synthesis of methylcellulose model copolymers with heterogeneous distribution and their solution properties. Cellulose 18, 105–115 (2011). https://doi.org/10.1007/s10570-010-9461-3

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