Evaluation of Selected Cellulose Macromolecular Properties after Its Chemical Treatment Using Size Exclusion Chromatography

Polymers (Basel). 2023 Jan 22;15(3):573. doi: 10.3390/polym15030573.

Abstract

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 ZnSO4·7H2O. The greatest depolymerization after treatment and after accelerated aging was caused by sulphates containing NH4+, Cu2+, and Fe3+ cations, with aging by NH4Cl and (NH4)2HPO4-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.

Keywords: cellulose; cellulose tricarbanilates; degradation; degree of polymerization; size exclusion chromatography; wood preservatives.

Grants and funding

This work was supported by the Slovak Research and Development Agency under contract No. APVV-16-0326 (50%) and by the VEGA Agency of the Ministry of Education, Science, Research and Sport of the Slovak Republic, No. 1/0117/22 (50%).