2024-03-28T18:14:04Zhttps://eprints.lib.hokudai.ac.jp/dspace-oai/requestoai:eprints.lib.hokudai.ac.jp:2115/862382022-11-17T02:08:08Zhdl_2115_20045hdl_2115_139Enhanced Self-Assembly and Mechanical Properties of Cellulose-Based Triblock Copolymers: Comparisons with Amylose-Based Triblock CopolymersKatsuhara, SatoshiTakagi, YasukoSunagawa, NaokiIgarashi, KiyohikoYamamoto, Takuya1000000271643Tajima, KenjiIsono, Takuya1000080291235Satoh, Toshifumiopen accessThis 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.self-assemblyblock copolymersamylosecellulosesustainable elastomersHerein, 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.American Chemical Society2021-07-26engjournal articleAMhttp://hdl.handle.net/2115/86238https://doi.org/10.1021/acssuschemeng.1c021802168-0485sustainable chemistry & engineering92997799788https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/86238/1/main_text_revise2_final2.pdfapplication/pdf1.13 MB2021-07-26