Lunn G, Sansone E B
PRI/DynCorp, Environmental Control and Research Program, NCI-Frederich Cancer Research and Development Center, MD 21702-1201.
Chemosphere. 1994 Oct;29(7):1577-90. doi: 10.1016/0045-6535(94)90287-9.
The degradation of 1,1-dimethylhydrazine (UDMH), a component of some rocket fuels, was investigated using atmospheric oxygen and hydrogen peroxide. The reactions were carried out in the presence and absence of copper catalysis and at varying pH. Reactions were also carried out in the presence of hydrazine, a constituent, along with UDMH, of the rocket fuel Aerozine-50. In the presence of copper, UDMH was degraded by air passed through the solution; the efficiency of degradation increased as the pH increased but the carcinogen N-nitrosodimethylamine (NDMA) was formed at neutral and alkaline pH. Oxidation was not seen in the absence of copper. Production of NDMA occurred even at copper concentrations of < 1 ppm. Oxidation of UDMH with hydrogen peroxide also gave rise to NDMA. When copper was absent degradation of UDMH did not occur at acid pH but when copper was present some degradation occurred at all pH levels investigated. The production of NDMA occurred mostly at neutral and alkaline pH. In general, higher concentrations of hydrogen peroxide and copper favored the production of NDMA. Dimethylamine, methanol, formaldehyde dimethylhydrazone, formaldehyde hydrazone, and tetramethyltetrazene were also produced. The last three compounds were tested and found to be mutagenic.
使用大气中的氧气和过氧化氢对某些火箭燃料成分偏二甲肼(UDMH)的降解情况进行了研究。反应在有铜催化和无铜催化的条件下以及不同pH值下进行。反应还在肼存在的情况下进行,肼是火箭燃料Aerozine - 50的一种成分,与UDMH一起存在。在有铜的情况下,通过溶液的空气可使UDMH降解;降解效率随pH值升高而增加,但在中性和碱性pH值下会形成致癌物N - 亚硝基二甲胺(NDMA)。在无铜的情况下未观察到氧化现象。即使铜浓度<1 ppm时也会产生NDMA。用过氧化氢氧化UDMH也会产生NDMA。当无铜时,在酸性pH值下UDMH不会降解,但当有铜时,在所研究的所有pH值水平下都会发生一定程度的降解。NDMA的产生主要发生在中性和碱性pH值下。一般来说,较高浓度的过氧化氢和铜有利于NDMA的产生。还产生了二甲胺、甲醇、二甲基肼甲醛、肼甲醛和四甲基四氮烯。对后三种化合物进行了测试,发现它们具有致突变性。