Synthesis of Energetic Polymers by the Introduction of Energetic Groups onto Polymeric Primary and Secondary Amines

Energetic polymers have been synthesised by the introduction of picryl groups onto linear polyethylenimine and polyvinylamine. The degree of substitution was 70–97% for polyethylenimine, depending upon the molecular weight of the polymer, and around 70% for polyvinylamine. N‐Picrylation of low molecular weight, model compounds was also studied. The results illustrate the influence of molecular weight on the chemical accessibility of a reaction site and reflect the difficulty of modelling polymer modification reactions using small molecules.