Indirect determination of partial depolymerization reactions in dialdehyde celluloses (DAC) by gel permeation chromatography of their oxime derivatives
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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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Date
2023-09
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Language
en
Pages
14
8677-8690
8677-8690
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Cellulose, Volume 30, issue 14
Abstract
Owing to a supposed quantitative transformation, oximation of dialdehyde cellulose (DAC) with hydroxylamine hydrochloride is commonly employed in chemical DAC analysis, e.g., for the determination of the degree of oxidation (DO) by titration or elemental analysis. In this study, this modification was utilized for the indirect determination of molecular weight distributions (MWD) by gel permeation chromatography (GPC). The presumably quantitative conversion of aldehyde groups in DAC to the corresponding oxime also breaks up the intermolecular and intramolecular hemiacetal crosslinks, which were associated with solubility issues in the DMAc/LiCl solvent system in previous studies. The limits of the procedure and the material's stability during oximation were investigated. For samples with a DO up to approximately 9% a good applicability was observed, before at higher DO values residual crosslinks led to solubility problems. The oximation/GPC protocol was used to examine the development of the MWD in the early stages of DAC formation under different reaction conditions. The time-dependent partial depolymerization of the polymer backbone was observed. Furthermore, the stability of DAC towards different pH conditions ranging from strongly acidic to strongly alkaline was tested. The depolymerization of DAC in alkaline media occurred with concomitant degradation of aldehyde moieties. In turn, DAC proved to be remarkably stable in acidic and neutral solutions up to a pH of 7.Description
Funding Information: This work was a part of the Academy of Finland's Flagship Programme under Projects No. 318890 and 318891 (Competence Center for Materials Bioeconomy, FinnCERES). The support by the Austrian Biorefinery Center Tulln (ABCT-II) is gratefully acknowledged. The authors thank Muhammad Awais for help in the visualization of the results. Publisher Copyright: © 2023, The Author(s).
Keywords
Beta elimination, Degradation, Hydroxyl amine, Periodate oxidation, Size exclusion chromatography
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Citation
Fliri, L, Simon, J, Sulaeva, I, Rosenau, T, Potthast, A & Hummel, M 2023, ' Indirect determination of partial depolymerization reactions in dialdehyde celluloses (DAC) by gel permeation chromatography of their oxime derivatives ', Cellulose, vol. 30, no. 14, pp. 8677-8690 . https://doi.org/10.1007/s10570-023-05412-4