Ynthesis and Properties of Cellulose Benzoyl Nitrates

The interaction of nitric acid esters of cellulose (low-nitrogen, with empirical formula C6H7O2(OH)0.87(ONO2)2.13 and nitrogen content of 11.56 %, and high-nitrogen, with empirical formula C6H7O2(OH)0.46(ONO2)2.54 and nitrogen content of 12.87 %) with benzoic acid chlorohydride was investigated. Using the quantum chemistry method, the reaction centers of interacting molecules were determined and the influence of the solvent on the intensity of benzoylation of cellulose nitroethers was evaluated. As a result of the research, high molecular weight compounds with novel properties were obtained. The nitrogen content of the benzoylation products is significantly reduced, for example, cellulose benzoyl nitrate - C10.93H14.56N0.52O5.89 synthesized on the basis of pyroxylin has a nitrogen content of 1.34%. In the course of elemental analysis for the content of carbon, hydrogen and nitrogen, rational formulas of reaction products were revealed. Based on the data obtained, it can be concluded that the duration of the process affects the reduction of nitrogen content and enhances the degree of electrophilic substitution of nitrate groups for benzoyl groups. It was determined that for the transesterification reaction of cellulose nitrates with benzoic acid chlorohydride the most suitable conditions are temperature 90°C and holding time 6 hours. With further increase in temperature and duration of the reaction, a significant decrease in the yield of the target product is observed, which is not economically feasible. The structural formulas of products were established using IR, 1H NMR, 13C NMR spectroscopy. By means of gel permeation chromatography and viscometric method the degree of polymer chain degradation was estimated. On the basis of physicochemical methods of research a generalized scheme of cellulose nitrate transformation including a set of several preferential parallel processes was proposed.