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  • Chemistry  (4)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 30 (1985), S. 897-914 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: 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 Ea 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.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 33 (1987), S. 247-282 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The kinetics of the thermal degradation of cellulose and modified cellulose, namely, cellulose phosphate, cellulose carbanilate, cellulose tosylate, chlorodeoxycellulose, bromodeoxycellulose, and iododeoxycellulose in air were studied by thermogravimetry and differential thermal analysis from ambient temperature to 700°C. The various thermodynamic functions for different stages of thermal degradation had been obtained following the procedure of Broido. The activation energies for the oxidative decomposition of cellulose and modified celluloses were found to be in the range 30-399 kJ mol-1. The infrared spectra of the residues of modified celluloses gave indication of formation of a compound containing P=O, P—O—P (only in the case of cellulose phosphate), C=C, and C=O groups in the final residual char. The EPR signals indicated the formation of trapped and stable free radicals in the thermal degradation of all the compounds, particularly halodeoxycelluloses showed generation of large amounts of trapped free radicals during the oxidative decomposition. Scanning electron micrographs of the thermally degraded cellulose derivatives show changes in the fibrillar structure, evolution of gasesous products, and film formation depending upon the nature of the substituent in the cellulose matrix. The mechanism of thermal degradation of these compounds has been proposed.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 183 (1982), S. 3003-3017 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the pyrolysis of cellulose and its derivatives (2,2-dichloropropionate and acetate) in nitrogen and air were studied by dynamic thermogravimetry and differential thermal analysis from ambient temperature to 600°C. From the resulting data various thermodynamic parameters could be obtained following the methods of Freeman and Carroll, Broido, and Dave and Chopra. The values of ΔE* for cellulose and its derivatives were found to be in the range 120 to 260 kJ · mol-1. However, the values of the free energy of activation for the degradation of cellulose and its derivatives are almost the same, i. e. 187 to 199 kJ · mol-1, indicating that the basic steps for the thermal degradation of cellulose and its derivatives are the same. Based on Scotney's work on the thermal degradation of cellulose triacetate, a mechanism for the thermal degradation of cellulose 2,2-dichloropropionate is proposed. The IR spectra of the pyrolysis residues of cellulose dichloropropionate indicate that dehydration takes place and a compound containing carbonyl groups is formed.
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 186 (1985), S. 2501-2512 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reactivity of primary and secondary hydroxyl groups of cellulose towards chlorotri(p-tolyl)methane in pyridine was studied in the temperature range of 60 to 100°C. The rate of reaction with the primary hydroxyl groups was found to be 43 times faster than that with the secondary hydroxyl groups of cellulose. The kinetic data showed that the reactivity of chlorotri(p-tolyl)methane towards primary hydroxyl groups of cellulose is higher than that of chlorotriphenylmethane (trityl chloride). The energies of activation for the reaction of primary and secondary hydroxyl groups of cellulose with chlorotri(p-tolyl)methane were found to be 39,6 and 43,1 kJ · mol-1, respectively. The reaction was observed to be pseudo first order.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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