Mass spectrometric kinetic studies on several azido polymers

• Published in: Combustion and flame Vol. 55; no. 2; pp. 203 - 211
• Main Authors: Farber, Milton, Harris, S.P., Srivastava, R.D.
• Format: Journal Article
• Language: English
• Published: New York, NY Elsevier Inc 01.02.1984; Elsevier Science
• Subjects: Applied sciences; Chemical reactions and properties; Degradation; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Ultraviolet irradiation; Organic azide; Model compound; Mass loss; Mass spectrum; Kinetics; Monomer; Activation energy; Thermal degradation
• ISSN: 0010-2180; 1556-2921
• DOI: 10.1016/0010-2180(84)90028-2

A mass spectrometric study of the thermal decomposition was made on four azido polymers which are possible new candidates for propellant formulations: bis azido methyl oxetane (BAMO), azido methyl oxetane (AMMO), azido oxetane (AZOX), and glycidyl azide polymer (GAP). All the polymers begin to decompose at approximately 120°C, with the primary decomposition mechanism being the rupture of the azide bond to release molecular nitrogen. Activation energies obtained were 42.7 kcal/mole for BAMO, 43.6 kcal/mole for AMMO, 40.1 kcal/mole for AZOX, and 42.2 kcal/mole for GAP. The polymeric E a values were close to those of a number of azido monomers having E a values of 39 to 40 kcal/mole. Secondary decomposition at higher temperatures (above 200°C) involved rupture of the carbon backbone smaller fragments. Irradiation at 366 nm (3.29 eV) ruptured the azide bonding with considerable cross-linking, transforming the polymer from a viscous liquid into a rubbery material.