Search

Abstract: DABCO mono-betaine (1,4-diazabicyclo[2.2.2]octane-1-acetate) forms a complex with HCl and water in the ratio 2:3:2. The crystals are triclinic, space group P . Two non-equivalent molecules of protonated DABCO mono-betaines form a homoconjugated cation through the short and asymmetric O·H·O hydrogen bond of 2.470(3)Å. Two chloride anions are involved in the N–H···Cl hydrogen bonds of 3.049(2) and 3.023(3)Å. The third chloride anion is solvated by the water molecules. The molecules of bis(1,4-diazoniumbicyclo[2.2.2]octane-1-acetate) trihydrochloride dihydrate are linked into comb-like chains by the hydrogen bond formed between water molecules of the neighboring complexes; the O(W)–H···O(W) distance is 2.920(5)Å. FTIR spectrum shows several broad bands attributed to the νO–H, νN–H and νO·H·O vibrations. The structure of three bis(1,4-diazoniumbicyclo[2.2.2]octane-1-acetate) hydrochlorides are optimized at the B3LYP/6-31G(d,p) level of theory and a theoretical IR spectrum is calculated. The values of pK a of DABCO, DABCO mono- and di-betaines are determined by the potentiometric titration of their hydrohalides. [Copyright &y& Elsevier]

The need for sustainable, biodegradable materials to address environmental challenges, such as oil-water separation, is growing. Cellulose-based absorbents offer an eco-friendly alternative to synthetic materials. However, their hydrophobicity must be enhanced for efficient application. In this study, cellulose-based sorbents derived from Kraft and half-bleached chemo-thermomechanical pulp (BCTMP) were hydrophobized using silanization and alkyl ketene dimer (AKD) techniques. Hydrophobic properties were successfully imparted using methyltrimethoxysilane (MTMOS), n-octyltriethoxysilane (NTES), and N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane (AATMS), with water contact angles ranging from 120° to 140°. The water sorption capacity was significantly reduced to below 1 g/g, whereas the oil sorption capacity remained high (19-28 g/g). The most substantial reduction in water vapor absorption (3-6%) was observed for the MTMOS- and AATMS-silanized samples. These results demonstrate the potential of hydrophobized cellulose-based sorbents as sustainable alternatives for oil-water separation, contributing to environmentally friendly water treatment solutions.

Phosphorylated cellulose can be an intrinsic flame retardant and a promising alternative for halogenated fire inhibitors. In this study, the mixture of di-ammonium hydrogen phosphate (DAP) and urea (U), containing phosphate and nitrogen groups, was applied to attain fire inhibitor properties. Functional groups of cellulose were grafted with phosphorous by keeping the constant molar ratio of 1/1.2/4.9 between anhydroglucose units of cellulose/DAP/U in different concentrations of bleached kraft pulp. Phosphorus concentrations were determined using the ICP hrOES method, and paper sheets were made using the Rapid Köthen apparatus. The tensile strength of phosphorylated cellulose increased twice compared with unmodified cellulose when the phosphorous concentration increased to 10,000 g/kg. An increase in the tensile index comes from the higher freeness of pulp and cross-linking of the phosphorous group between cellulose fibers. Remarkable fire retardancy effects were achieved in cellulose concentrations above 5 wt%. The raised phosphorous concentration above 10,000 g/kg due to the phosphorylation process caused the formation of a char layer on a cellulose surface and the nonflammable gas emission. That effect was indirectly confirmed by reducing the combustion temperature and HRR by 50 and 45%, respectively. Due to increasing phosphorus concentration in cellulose sheets, cellulose's fire and strength properties increased significantly.

Modifying natural polymers with silicones gives new possibilities for packaging products and waste management. In this study, the innovative papers produced were altered following the reaction of polysaccharides and organosilicon compounds. The susceptibility of the studied material to biodegradation caused by a brown-rot fungus was assessed. Strength properties by tensile strength and dynamic mechanical analysis and hydrophobic properties by water uptake test and water contact angle analysis were evaluated. Moreover, elemental analysis by ICP method was controlled. The durability against fungi and the hydrophobic properties were increased by the modification. The fungal decay resistance of the silanized paper was reduced by water storage, which allows for managing paper waste. Cellulose-based paper treated with starch-modified methyltrimethoxysilane showed potential as a packaging material due to its reduced water uptake. Possible application areas could be corrugated boxes, cellulose thermoformed products for electronics, and food packaging. However, the water-repellent effect is limited to short-term exposure in humid conditions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

This article describes how crystalline or fibrous nanocellulose influences the mechanical properties of paper substrate. In this context, we used commercially available cellulose nanocrystals, mechanically prepared cellulose nanofibers dispersed in water or ethanol, and carboxy cellulose nanofibers. Selective reinforcement of the paper treated with the nanocellulose samples mentioned above was observed. The change in the fibre structure was assessed using scanning electron microscopy, roentgenography, and spectroscopy techniques. In addition, the effect of nanocellulose coating on physical properties was evaluated, specifically tensile index, elongation coefficient, Elmendorf tear resistance, Bendtsen surface roughness, Bendtsen air permeability, and bending strength. It can be concluded that the observed decrease in the strength properties of the paper after applying some NC compositions is due to the loss of potential disturbances in hydrogen bonds between the nanocellulose dispersed in ethanol and the paper substrate. On the other hand, significantly increased strength was observed in the case of paper reinforced with nanocellulose functionalized with carboxyl groups.

Starch is an inexpensive, easily accessible, and widespread natural polymer. Due to its properties and availability, this polysaccharide is an attractive precursor for sustainable products. Considering its exploitation in adhesives and coatings, the major drawback of starch is its high affinity towards water. This study aims to explain the influence of the silane-starch coating on the hydrophobic properties of paper. The analysis of the organosilicon modified starch properties showed an enhanced hydrophobic behavior, suggesting higher durability for the coatings. Molecules of silanes with short aliphatic carbon chains were easily embedded in the starch structure. Longer side chains of silanes were primarily localized on the surface of the starch structure. The best hydrophobic properties were obtained for the paper coated with the composition based on starch and methyltrimethoxysilane. This coating also improved the bursting resistance and compressive strength of the tested paper. A static contact angle higher than 115° was achieved. PDA analysis confirmed the examined material exhibited high barrier properties towards water. The results extend the knowledge of the interaction of silane compositions in the presence of starch.

The subject of this work was to characterize the catalytic course of the linseed oil silylation reaction with vinyltrimethoxysilane (VTMOS), carried out under elevated pressure and temperature conditions, and an explanation of the reasons for rapid gelation of the reaction product. To explain and describe the process, analytical methods were used, i.e., 1 H and 13 C NMR (nuclear magnetic resonance), GC-FID (gas chromatography coupled with flame ionisation detection), and GPC (gel permeation chromatography). Reaction products were monitored after 3, 6 and 12 h. The molar mass of the VTMOS-modified oil in only 3 h was comparable with the molar mass of the product obtained by conventional polymerisation. An increase in the reaction time resulted in further transformations resulting from the hydrolysis and condensation reactions taking place. In contrast to reactivity of soybean oil, the silanisation of linseed oil occurred much faster and without the need for cross-linking catalysts. The reason for the high reactivity of linseed oil to VTMOS and rapid gelation of the resulting product was primarily the amount of double bonds present in linseed oil and their high availability, in particular the double bond in the acid linolenic acid located at the C16 carbon.

Due to the wider use of nanocellulose in various areas of economic life, better and more optimal methods of obtaining nanocellulose are constantly being sought. Therefore, an attempt was made to evaluate the hybrid cellulose treatment, based on the use of a chemical method combined with an ultrasound of medium frequency. The study employs two different starting materials (Södra Black R cellulose or microcrystalline cellulose), two types of chemical pre-treatments (acid hydrolysis or oxidation), and two sonication durations. It was found that the reduction fiber cross-sectional dimensions was the result of prolonged exposure of cellulose to the ultrasound. From Södra Black R and the microcrystalline cellulose nanometer scale, structures were obtained in the form of isolated fibers. The TEMPO reagent accelerated the degradation process of two cellulose varieties due to its oxidizing character. The resulting products had nanofibrous structures. Cellulose degradation as a result of the combined action of sonication and TEMPO activity progressed gradually. Places of fiber degradation were characterized by their longitudinal breakage and initiated the next stages of the defibering process.

It can be found that reaction mechanisms and interactions between wood and organosilicone compounds have not been sufficiently explored. The aim of the study was to determine bonds formed between either cellulose or lignin and methyltrimethoxysilane (MTMOS) during a catalytic silanization reaction. Silanization was performed in the presence of two catalysts of a diverse mechanism of functionalization: aluminum acetylacetonate (Al(acac) 3 ) and acetic acid (AcOH). For this purpose, FT-IR, 13 C and 29 Si NMR techniques were used. Cellulose silanization efficiency without a catalyst was unlikely. Lignin undergoes a silanization reaction with alkoxysilanes much easier than cellulose. The results showed new bonds between biopolymers and the silanising agent. The new bonds were confirmed by signals at the FT-IR spectra, e.g., 770 cm -1 and 1270 cm -1 (Si-CH 3 ), and at the NMR signal coming from the T 1 , T 2 and T 3 structures. Efficiency of reaction was confirmed by atomic absorption spectroscopy (AAS) analysis.