The reductive amination of dialdehyde cellulose (DAC) with 2-picoline borane was investigated for its applicability in the generation of bioderived thermoplastics. Five primary amines, both aliphatic and aromatic, were introduced to the cellulose backbone. The influences of the side chains on the course of the reaction were examined by various analytical techniques with microcrystalline cellulose as a model compound. The obtained insights were transferred to a 39%-oxidized softwood kraft pulp to study the thermal properties of thereby generated high-molecularweight thermoplastics. The number-average molecular weights (M n ) of the diamine celluloses, ranging from 60 to 82 kD, were investigated by gel permeation chromatography. The diamine celluloses exhibited glass transition temperatures (T g ) from 71 to 112 °C and were stable at high temperatures. Diamine cellulose generated from aniline and DAC showed the highest conversion, the highest T g (112 °C), and a narrow molecular weight distribution (D̵ of 1.30).
The average molecular weights (MWs) and molecular-weight distributions of lignin dissolved during different stages of the industrial totally chlorine-free (TCP) bleaching (OXZE op AEpS) of hardwood kraft pulp were compared by gel permeation chromatography (GPC) with an adequate calibration. The weight-average and number-average MWs of the total effluents from the different stages were within the ranges M w ~ 700-5,350 and M n -350-1,350. The average MWs of lignins from the stages Z and A (M w 7 00-1,500) were much lower than those (M w ~ 2,000-5,350) of lignins from other bleaching stages. GPC results for fractions separated by analytical ultrafiltration (UF) showed the average MWs of these fractions to be significantly lower than would be expected from cutoff values of the membranes.
Borohydride reduction of dialdehyde cellulose (DAC) is a promising strategy to generate dialcohol cellulose as bio-based alternative to petroleum-based materials. However, the degradation of the polymer backbone according to β-elimination mechanisms limits the practical applications of the reaction. Therefore, we aimed at optimizing the process to suppress degradation reactions by varying reaction time, pH, and reagent stoichiometry. The degree of oxidation (DO) of the DAC intermediates significantly impacts the yields and molecular weights of the isolated dialcohol celluloses, with a “leveling-off” effect at higher DO values. Increasing the amount of sodium borohydride can minimize—but not entirely prevent—chain scissions. Lowering the pH value during reduction slows down the degradation but results in incomplete conversion of the aldehyde functionalities. Our study provides valuable insights into the consequences of side reactions during borohydride reduction of DAC as well as into chemistry and analysis of the dialdehyde cellulose/dialcohol cellulose system.
Graphical abstract
About a dilemma in cellulose chemistry: Dialcohol cellulose derived by periodate oxidation and subsequent borohydride reduction of cellulose has received increasing attention in the development of sustainable thermoplastic materials. The present study highlights the challenge of suppressing β-elimination and favoring the reduction pathway to optimize reaction conditions and minimize chain degradation.
The effect of the partial removal of xylan on unbleached and bleached birch kraft pulps was investigated by Fourier transform infrared (FTIR) microspectroscopy and the resulting data were analyzed by multivariate data analysis, i.e., principal component analysis (PCA) and maximum likelihood principal component analysis (MLPCA). Isolated model substances (xylan, cellulose and lignin) were used to calibrate these methods. Clear chemical changes in the relative proportions of the main constituents and functional groups on the pulp fiber surface were observed as a function of the amount of xylan removed. In addition, due to the partial removal of xylan, indications of some physical changes were observed.
Keywords
Silver birchBetula pendula Kraft pulp Xylanase treatment FTIR microspectroscopy MLPCA PCA Brought to you by |
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