Thermal degradation of cellulose and its phosphorylated products in air and nitrogen

The thermal degradation of cellulose and its phosphorylated products (phosphates, diethylphosphate, and diphenylphosphate) were studied in air and nitrogen by differential thermal analysis and dynamic thermogravimetry from ambient temperature to 750°C. From the resulting data various thermodynamic parameters were obtained following the methods of Broido and Freeman and Carroll. The values of E_a for decomposition for phosphorylated cellulose were found to be in the range 55–138 kJ mol^?1 in air and 85–152 kJ mol^?1 in nitrogen and depended upon the percent of phosphorus contents in the samples. The mass spectrum of cellobiose phosphate indicated the absence of the molecular ion, indicating that the compound was thermally unstable. The IR spectra of the pyrolysis residues of cellulose phosphate gave indication of formation of a compound having C?O and P?O groups. A fire retardancy mechanism for the thermal degradation of cellulose phosphate has been proposed.