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Mass spectrometry analysis of hexamethylene triperoxide diamine by its decomposition products

Hexamethylene triperoxide diamine (HMTD) is a well known amine peroxide that starts to decompose at ambient temperature. At 40°C HMTD began to break up into volatile pungent compounds, including trimethyl amine. The production of these compounds could be useful for the vapor detection of HMTD by common techniques such as GC-MS and IMS. GC-MS analysis was performed and several volatile amines could be detected including initial reagents, such as hexamine. IMS produced an alarm indicating the presence of other compounds. Open-Air Chemical Ionization (OACI)-Time of Flight (TOF)-Mass Spectroscopy was the most useful technique for the analysis of HMTD. Even at high temperatures (250°C), it was possible to detect the molecular ion at m/z 209.078. Other fragments observed in the mass spectrum were the loss of formaldehyde at m/z 179.069 and the loss of hydrogen peroxide at m/z 145.060. A mixture of 30 ppb of HMTD and triacetone triperoxide (TATP) was successfully analyzed by OACI-TOF-MS, thus demonstrating its feasibility for trace analysis of organic peroxides and related compounds.