INVESTIGATION OF REACTIONS OF INTERACTION OF CELLULOSE NITRIC ESTERS WITH CARBOXYLIC ACID CHLORIDES

The chemical interaction of high-nitrogen cellulose ether with acetic, propionic, butyric and isobutyric acids has been studied. The general laws and features of the electrophilic substitution of functional groups of cellulose nitroesters are revealed. The preferred directions of the chemical interaction of cellulose nitrate with carboxylic acid chlorides are established: O-acylation of nitrate and hydroxyl groups; O-acylation of the glucopyranose ring; O-acylation of the ether bond with depolymerization of the chain of an SC molecule; hydrolysis of nitrate groups; destruction of the chain of a macromolecule of nitric acid ester with the formation of water-soluble organic compounds. The structure, properties and possibilities of using synthesized mixed cellulose ethers were studied. Effective methods have been developed for the chemical modification of cellulose nitrates with carboxylic acid chlorides. The probable directions of the reaction of the interaction of cellulose nitrates with electrophilic reagents are predicted based on quantum-chemical calculations of point charges on the atoms of the reacting molecules. The reactivity of highly substituted cellulose nitrates in reactions with carboxylic acid chlorides has been established. The optimal conditions for the interaction of cellulose nitrates with carboxylic acid chlorides have been identified and a mathematical model of the reaction kinetics has been constructed. The possibility of a directed change in the composition of chemically modified cellulose nitrates depending on the synthesis conditions has been established. As a result of the combined use of physicochemical research methods, the chemical composition was determined and the structure of the synthesized compounds was determined: cellulose acetyl nitrates, cellulose propionyl nitrates, cellulose butyryl nitrates, and cellulose isobutyryl nitrates. Using gel chromatography, it was found that the molecular weight characteristics of the synthesized samples are directly dependent on the conditions of their synthesis. It was found that electrophilic substitution of the functional groups of cellulose nitrate proceeds more intensively in the pyridine medium.

Dissolving pulp production: Cellulases and xylanases for the enhancement of cellulose accessibility and reactivity

Dissolving pulps are high-grade cellulose pulps that have minimum amount of non-cellulosic impurities. Dissolving pulps are the basic source for the manufacturing of several cellulosic products such as viscose, lyocell, cellulose acetates, cellulose nitrates, carboxymethyl-cellulose, etc. Dissolving pulps are mainly manufactured by pre-hydrolysis kraft and acid sulphite pulping. A high reactivity of dissolving pulps is desirable for its eco-friendly utilization for several purposes. Several approaches including mechanical, chemical, ultrasonic, and enzymatic treatments have been employed for the improvement of pulp reactivity. This review mainly focussed on pulp reactivity improvement through enzymatic approaches. Cellulases and xylanase have been proved effective for the improvement of pulp reactivity of dissolving pulp from different sources. The different combinations of cellulase, xylanase, and mechanical refining have been tested and found more effective rather than the single one.

Miscanthus × Giganteus var. KAMIS as a New Feedstock for Cellulose Nitrates

Due to the limited volumes of conventional sources of cellulose (cotton and wood), research centered on producing the most competitive science-driven products – cellulose nitrates – from new, domestic, easily renewable feedstocks is extremely relevant. The review of scientific literature corroborates the lack of data on the feasibility to obtain cellulose nitrates from Miscanthus, except for the authors’ publications. Here we suggest a tree-like industrial crop, Miscanthus var. KAMIS, growing with an yield of up to 20 t/ha a year on industrial plantations in Kaliningradskaya, Kaluzhskaya and Yaroslavskaya Oblasts and in Primorskiy Krai. A pulp sample derived from Miscanthus var. KAMIS by the nitric-acid process exhibits a high α-cellulose content of 96 % and degree of polymerization of 1350. Under optimum synthesis conditions previously identified for unconventional feedstocks, a cellulose nitrate sample was synthesized by treating the pulp with commercially available mixed acid and had the following functional characteristics: 11.26 % nitrogen content, 52 mPа∙s viscosity, and – 95 % solubility on alcohol-ester mixture. Morphological features of pulp and cellulose nitrate samples were characterized by scanning electron microscopy. IR spectroscopy revealed the presence of functional groups in pulp samples (3411, 2913, 1637, 1429, 1369, 1317, 1161, 700-500 cm-1) and cellulose nitrate samples (2553, 1642, 1276, 830, 746, 680 cm-1), which allow those samples to be identified as cellulose and nitrate cellulose esters, respectively. It was found by scanning electron microscopy that the cellulose nitrate sample matches industrial Colloxylines by the onset temperature of decomposition (199 °С) and specific head of decomposition (8,43 kJ/g). The practical importance of this study is that we experimentally justify the feasibility to utilize the new, unconventional, domestic, easily renewable feedstock, Miscanthus var. KAMIS, as a precursor of high-quality cellulose nitrates

BIOSYNTHESIS AND FUNCTIONALIZATION OF BACTERIAL NANOCELLULOSE FOR INDUSTRIAL APPLICATIONS

This study aimed at scale-up the biosynthesis of bacterial nanocellulose (BNC) and its functionalization with the production of cellulose nitrates (CNs).

AUTOCLAVING CELLULOSE NITRATES OBTAINED FROM FRUIT SHELLS OF OATS

Besides the targeted viscosity decrease, the high-temperature autoclaving of cellulose nitrates (CNs) can provide one of the key properties – chemical stability – which governs the operational process safety and guaranteed shelf life of CN-based products. Here we report the study results of the autoclaving of cellulose nitrates derived by esterification of pulp with mixed sulfuric-nitric acids. The pulp was obtained from an easily renewable domestic feedstock – oat hulls – agro-industrial residue. On the basis of experiments, regression relationships are suggested herein that enable the prediction of basic properties of CNs, depending on autoclaving time. The optimum high-temperature autoclaving time was identified that allows oat-hull CNs to be produced with the following characteristics: 12.14% nitrogen content, 12 mPa·s viscosity and 98% solubility in alcohol-ether mixture, which are similar to the characteristics of dinitrocellulose (Colloxyline-N). Ampule chromatography confirmed that the resultant CNs had a high chemical stability. The quantity of nitrogen oxide from thermal decomposition of CNs (90 °С, 192 h) was found to be 0.35 ml/g and was not above the permissible level for dinitrocellulose. Differential scanning calorimetry revealed that the oat-hull CNs are characterized by a high onset temperature of decomposition (200 °С) and a high specific heat of decomposition (7.36 kJ/kg), indicating a high chemical purity of the resultant product. The findings presented herein justify the use of oat-hull CNs in the manufacture of gun-propellant grains and composite explosives.

Features of structure and properties of hemp cellulose nitrates

Comprehensive studies of the structural, molecular and physico-chemical properties of cellulose nitrates from hemp fiber were carried out using modern research methods: capillary viscometry, IR Fourier spectroscopy, X-ray diffraction, gel permeation chromatography. The results of the study revealed features of the influence of inter- and intramolecular interactions in cellulose macromolecules from various types of fiber, the degree of crystallinity of the initial material, and the degree of polydispersity on the formation of qualitative characteristics of hemp cellulose nitrates.

Oat-hull cellulose nitrates for explosive compositions

Cellulose nitrates similar in basic properties to high-viscosity lacquer-grade Colloxyline were synthesized by esterification of pulp with mixed acid. The pulp was isolated from the easily renewable domestic feedstock - oat hulls - the agro-industrial waste. The cellulose nitrate test samples were comparatively evaluated. Infrared and 13C NMR spectroscopies confirmed the chemical structures were identical. It was established by differentiated scanning calorimetry and ampule chromatography that the samples had a high chemical purity. The cellulose nitrates were found to have satisfactory impact and friction sensitivities of 50 mm and 1200 kgf/cm2 and exhibit a good chemical compatibility and a high chemical stability when blended with plasticizers. The findings suggest that it is advisable to use oat-hull cellulose nitrates as the component of composite explosives.