Regioselective synthesis of cellulosic janus bottlebrushes with polystyrene and poly (ε-caprolactone) side chains and their solid-state microphase separation

Sakakibara, Keita; Ishida, H.; Kinose, Yuji; Tsujii, Yoshinobu

doi:10.1007/s10570-021-03964-x

Cited by 5 publications

(4 citation statements)

References 51 publications

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“…In this regard, position 6 has been reacted with 4pentynylcarboxylic acid after detritylation, which can be further treated by click chemistry (azide/alkyne cycloaddition). This concept can also be applied for the synthesis of mixed derivatives bearing polystyrene and poly(-caprolactone) (Sakakibara et al 2021). The products were shaped to films.…”

Section: 3-o-functionalized Polysaccharide Derivativesmentioning

confidence: 99%

Structure design of polysaccharides by selective conversion: Old hat or topical?

Koschella

Heinze

2023

BioRes

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The functionalization pattern in polysaccharide derivatives is an important factor that determines their properties and, thus, their functions in applications. Regioselectively functionalized polysaccharide derivatives are used in material science because they may form lamellar structures in microscale by self-assembling. Intrinsically chiral polysaccharide derivatives are used for the separation of enantiomers by chromatography, and the separation efficiency is influenced by the regioselective distribution of substituents attached. Due to the multi-functionality of polysaccharides, their derivatization reactions usually yield products with random distribution of substituents. Thus, establishment of unambiguous structure-property relationships cannot be achieved. This review article summarizes recent developments in this topic. In addition to the blocking group techniques, synthesis methods applying activating substituents will be summarized. Moreover, the reaction medium itself may direct the substituent in a certain position without laborious multistep reactions.

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Section: 3-o-functionalized Polysaccharide Derivativesmentioning

confidence: 99%

Structure design of polysaccharides by selective conversion: Old hat or topical?

Koschella

Heinze

2023

BioRes

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“…One is microphase separation of high χ–low N linear block copolymers, − where χ is the Flory–Huggins interaction parameter and N is degree of polymerization. Another is microphase separation of the side or graft chains of polymers including (1) random or alternating copolymers, − (2) double brush (Janus graft) (co)polymers, − (3) brush polymers bearing block side chains, , (4) periodic graft copolymers, − and (5) homopolymers containing polar functional groups. − In the latter approaches, the domain spacing of the phase-separated structures is often controlled by tuning the copolymer composition or side chain structures. Therefore, common (co)polymers with broad molecular weight distribution, typically prepared by free radical polymerization, can also be used for the construction of well-defined nanostructures, although the former approach requires block copolymers with narrow molecular weight distribution for controlling the domain structures and spacing.…”

Section: Introductionmentioning

confidence: 99%

Microphase Separation of Cationic Homopolymers Bearing Alkyl Ammonium Salts into Sub-4 nm Lamellar Materials with Water Intercalation Channels

Sujita,

Imai,

Ouchi

et al. 2023

Macromolecules

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“…Recently, another approach for the synthesis of regioselectively substituted polysaccharide-based copolymers was published. In this work, Tsuji et al also employed the hydroxyl groups at C2 and C3 of the anhydroglucose unit for the polymerization reaction of ε-caprolactone, while polystyrene was grafted subsequently to the hydroxyl group at C6 via click chemistry for the production of cellulose-based Janus bottlebrushes [ 21 ]. Alternatively, copolymers were prepared by a “grafting to” approach using methyl-polyethyleneglycol iodide in a nucleophilic substitution in order to obtain the C2 and C3-substituted cellulose derivative [ 22 ], which can also be further modified using grafting reactions, e.g., via click reactions with modified polystyrene as mentioned above [ 23 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Functional Cellulose–Ether-Based PCL- and PLA-Grafts-Copolymers

2023

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The use of biodegradable materials such as cellulose and polyesters can be extended through the combination, as well as modification, of these biopolymers. By controlling the molecular structure and composition of copolymers of these components, it should also be possible to tailor their material properties. We hereby report on the synthesis and characterization of cellulose-based graft copolymers with a precise molecular composition and copolymer architecture. To prepare such materials, we initially modified cellulose through the regioselective protection of the 6-OH group using trityl chloride. The 6-O protected compound was then alkylated, and deprotection at the 6-OH group provided the desired 2,3-di-O-alkyl cellulose compounds that were used as macroinitiators for ring opening polymerization. Regioselective modification was hereby necessary to obtain compounds with an exact molecular composition. Ring opening polymerization, catalyzed by Sn(Oct)2, at the primary 6-OH group of the cellulose macroinitiator, using L-lactide or ε-caprolactone, resulted in graft copolymers with the desired functionalization pattern. The materials were characterized using Fourier-transform infrared spectroscopy, 1H- and 13C- nuclear magnetic resonance spectroscopy, size exclusion chromatography as well as X-ray diffraction, and differential scanning calorimetry. PCL-based copolymers exhibited distinct melting point as well as a crystalline phase of up to 47%, while copolymers with PLA segments were highly amorphous, showing a broad amorphous reflex in the XRD spectra, and no melting or crystallization points were discernible using differential scanning calorimetry.

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Regioselective synthesis of cellulosic janus bottlebrushes with polystyrene and poly (ε-caprolactone) side chains and their solid-state microphase separation

Cited by 5 publications

References 51 publications

Structure design of polysaccharides by selective conversion: Old hat or topical?

Structure design of polysaccharides by selective conversion: Old hat or topical?

Microphase Separation of Cationic Homopolymers Bearing Alkyl Ammonium Salts into Sub-4 nm Lamellar Materials with Water Intercalation Channels

Synthesis and Characterization of Functional Cellulose–Ether-Based PCL- and PLA-Grafts-Copolymers

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