Jurczyková Tereza, Kačík František, Čabalová Iveta, Hájková Kateřina
Department of Wood Processing and Biomaterials, Faculty of Forestry and Wood Sciences, Czech University of Life Sciences Prague, Kamýcka 129, 16000 Prague, Czech Republic.
Department of Chemistry and Chemical Technologies, Faculty of Wood Sciences and Technology, Technical University in Zvolen, T. G. Masaryka 24, 96001 Zvolen, Slovakia.
Polymers (Basel). 2023 Jan 22;15(3):573. doi: 10.3390/polym15030573.
This work evaluates the effect of using selected inorganic chemicals as the main components of waterborne wood preservative systems on the degradation of the cellulose constituent in wood from model samples. The polymeric properties of cellulose and the homogeneity of the degradation process primarily reflect very well the degree of cellulose deterioration. Whatman papers, as pure cellulose model samples, were impregnated with 10 different 5 wt% solutions of inorganic salts and distilled water and consequently subjected to wet-thermal accelerated aging (T = 85 °C, RH = 65%, for 30 days). The samples were then derivatized to cellulose tricarbanilates (CTCs) through two different procedures (by precipitation in a methanol-water mixture/by evaporation of pyridine from the reaction mixture) and finally analyzed using size exclusion chromatography (SEC). Chemically treated and aged cellulose samples showed different changes in the degree of polymerization (DP) and polydispersity (PD) in terms of untreated non-aged standard caused by different ongoing degradation reactions, such as dehydration, hydrolysis, oxidation, and crosslinking. In general, the lowest degradation rate after treatment by chemicals and after accelerated aging was observed in samples treated by borates, NaCl, and ZnSO·7HO. The greatest depolymerization after treatment and after accelerated aging was caused by sulphates containing NH, Cu, and Fe cations, with aging by NHCl and (NH)HPO-treated samples also leading to significant depolymerization. The higher DP values are linked to the precipitated method of CTC preparation, though not for chlorides and phosphates. PD is also generally higher in precipitated and aged samples and is heavily influenced by the presence of low molecular weight products. This paper brings new insights regarding the complex evaluation of the polymeric properties of degraded cellulose by considering all important factors affecting the sample and the analysis itself through the use of statistics. From the statistical point of view, the influences of all factors (solution, aging, method) and their interactions (except aging*method) on DP are statistically significant. The influence of the sample processing method used for analysis of the desired results becomes important mainly in practice. This work recommends the evaporation method for more accurate description of more degraded cellulose.
本研究评估了使用选定的无机化学品作为水性木材防腐体系的主要成分对模型样品木材中纤维素成分降解的影响。纤维素的聚合特性和降解过程的均匀性很好地反映了纤维素的降解程度。作为纯纤维素模型样品的Whatman滤纸,用10种不同的5 wt%无机盐溶液和蒸馏水浸渍,然后进行湿热加速老化(T = 85 °C,RH = 65%,持续30天)。然后通过两种不同的程序(在甲醇 - 水混合物中沉淀/从反应混合物中蒸发吡啶)将样品衍生化为三氨基甲酸纤维素酯(CTCs),最后使用尺寸排阻色谱(SEC)进行分析。由于不同的降解反应(如脱水、水解、氧化和交联)持续进行,化学处理和老化的纤维素样品与未处理的未老化标准相比,在聚合度(DP)和多分散性(PD)方面表现出不同的变化。一般来说,硼酸盐、NaCl和ZnSO₄·7H₂O处理的样品在化学处理和加速老化后的降解率最低。处理和加速老化后最大的解聚是由含有NH₄⁺、Cu²⁺和Fe³⁺阳离子的硫酸盐引起的,NH₄Cl和(NH₄)₂HPO₄处理的样品老化也导致了显著的解聚。较高的DP值与CTCs制备的沉淀法有关,不过氯化物和磷酸盐除外。沉淀和老化样品中的PD通常也较高,并且受到低分子量产物的严重影响。本文通过考虑影响样品和分析本身的所有重要因素并使用统计学方法,为降解纤维素的聚合特性的复杂评估带来了新的见解。从统计学角度来看,所有因素(溶液、老化、方法)及其相互作用(老化*方法除外)对DP的影响具有统计学意义。用于分析所需结果的样品处理方法的影响主要在实际应用中变得重要。这项工作推荐使用蒸发法来更准确地描述降解程度更高的纤维素。
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