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Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers
Title: | Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock Copolymers |
Authors: | Katsuhara, Satoshi Browse this author | Takagi, Yasuko Browse this author | Sunagawa, Naoki Browse this author | Igarashi, Kiyohiko Browse this author | Yamamoto, Takuya Browse this author | Tajima, Kenji Browse this author →KAKEN DB | Isono, Takuya Browse this author | Satoh, Toshifumi Browse this author →KAKEN DB |
Keywords: | self-assembly | block copolymers | amylose | cellulose | sustainable elastomers |
Issue Date: | 26-Jul-2021 |
Publisher: | American Chemical Society |
Journal Title: | sustainable chemistry & engineering |
Volume: | 9 |
Issue: | 29 |
Start Page: | 9779 |
End Page: | 9788 |
Publisher DOI: | 10.1021/acssuschemeng.1c02180 |
Abstract: | Herein, we compared the microphase-separation behavior and mechanical properties of cellulose- and amylose-based block copolymers (BCPs). Various cellooligosaccharide triacetate-b-poly(delta-decanolactone)-b-cellooligosaccharide triacetates (AcCel(n)-b-PDL-b-AcCel(n)s), which are cellulose-based ABA-type BCPs, with PDL molecular weights of approximately 5, 10, and 20 kg mol(-1) and PDL volume fractions of 0.65, 0.77, and 0.87, were synthesized from alpha,omega-diazido-end-functionalized PDLs and propargyl-end-functionalized cellooligosaccharide triacetates via click chemistry. We adopted the cellodextrin-phosphorylase-mediated oligomerization of alpha-D-glucose-1-phosphase in the presence of a propargyl-end-functionalized cellobiose primer to synthesize the functional cellooligosaccharide segment. The maltooligosaccharide triacetate-b-poly(delta-decanolactone)-b-maltooligosaccharide triacetate (AcMal(n)-b-PDL-b-AcMal(n)s) amylose counterparts were also synthesized in a similar manner. Small-angle X-ray scattering experiments and atomic force microscopy revealed that AcCel(n)-b-PDL-b-AcCel(n)s are more likely to microphase-separate into ordered nanostructures compared to AcMal(n)-b-PDL-b-AcMal(n)s, despite their comparable chemical compositions and molecular weights. Furthermore, AcCel(n)-b-PDL-b-AcCel(n)s exhibited significantly superior mechanical performance compared to their amylose counterparts under tensile testing, with Young's modulus and stress at break of AcCel(n)-b-PDL10k-b-AcCel(n) being 2.3 and 1.8 times higher, respectively, than those of AcMal(n)-b-PDL10k-b-AcMal(n). The enhanced microphase-separation and mechanical properties of AcCel(n)-b-PDL-b-AcCel(n)s were found to be attributable to the stiffness and crystalline nature of the AcCel(n) segments. These results demonstrate the advantages of using cellulose derivatives to synthesize novel biofunctional materials. |
Rights: | This document is the Accepted Manuscript version of a Published Work that
appeared in final form in ACS sustainable chemistry & engineering,
copyright c American Chemical Society after peer review and technical editing by
the publisher.
To access the final edited and published work see
https://pubs.acs.org/articlesonrequest/AOR-QZU4XGDVP8UX3PJGNKQT. |
Type: | article (author version) |
URI: | http://hdl.handle.net/2115/86238 |
Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 佐藤 敏文
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