Review : Auto-oxidation of aliphatic polyamides
Résumé
The literature on oxidation kinetics of polyamides and model compounds has been reviewed in order to try to extract suitable information for non-empirical kinetic modeling. Polyamide characteristics are systematically compared to polyolefin ones, these latter being more extensively studied. From kinetic analysis point of view, it is shown that oxidation attacks predominantly a amino methylenes of which C eH bond is considerably weaker than the other methylenes. As a result, propagation by H abstraction is considerably faster in polyamides than in polyethylene for instance. Termination by radical combination is also very fast. Another cause of PA oxidizability is the instability of a amino hydroperoxides linked to the inductive effect of nitrogen. This instability is responsible for many key features of oxidation kinetics especially the absence of induction period. The main stable oxidation products are imides resulting from disproportionation processes meanwhile chain scissions resulting from rearrangements of a amino alkyls by b-scission are also significant process although their yield appears lower than in polyolefins.
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