Glycidyl azide polymers (GAP) are being used as energetic binders in explosives and propellant formulations. The elastomeric properties of the binder are normally given by a urethane‐based reticulation process involving isocyanate compounds. Alternatively, azides bearing polymers can be cured by reaction with dialkynes as a result of the so‐called “click chemistry” process. This work investigates the reaction kinetics of GAP with five different dialkynes: one ether, three esters and one alkane derivative. The reactivity parameters of these compounds towards low molecular weight GAP have been established, along with the corresponding exotherm for each curing reaction. In light of the energetic nature of GAP, these results will allow the use of the same dialkyne compounds on a larger scale by making it possible to predict the behavior of these reacting mixtures and to allow a safe control over their exothermic curing process.

Azido polymers find use as energetic binders in a variety of composite explosive and propellant applications, but few azido polyesters have previously been reported: a method is introduced for the preparation of two azido polycarbonates, poly(2,2'-bisazidomethyl-1,3-propyl carbonate) and poly(3-azido-1,2-propyl carbonate), possible binder candidates for energetics applications. The preparation method for these polymers involves a two-step synthesis starting from the bulk polymerization of the commercially sourced diols with diphenyl carbonate in the presence of lanthanum (III) acetylacetonate as a neutral catalyst, and subsequent azidation in cyclohexanone. The physical and thermal characteristics of each are reported, indicating properties similar to other azido-polymers. The thermal and mechanical properties of cured azido polyester resin mixtures are the subject of ongoing research.

Triazole cross‐linked energetic polymer networks obtained from the reaction of dialkyne curing agents with glycidyl azide polymers (GAP) or poly(2,2‐[bisazidomethyl]propane‐1,3‐diyl carbonate) (poly[BAMPC]) were studied, and their thermal and mechanical properties are reported. The dialkynes studied include bis(propargyl)ether (BPE), bis(propargyl)malonate (BPM), and 4,4’‐diacyanohepta‐1,6‐diyne (DCHD), three compounds previously described as curing agents for glycidyl azide pre‐polymers. The cured polymer networks display a wide range of properties dependent on the nature of the azido pre‐polymer, the nature of the dialkyne, the alkyne/azide molar ratio, and the molecular weight of the pre‐polymer used. Results confirm that the three dialkynes are effective curing agents able to form rigid networks out of either pre‐polymer and that the lighter molecular weight BPE and DCHD both improve mechanical properties of cured networks with less dilution of the system's energetic content. Triazole cross‐linked poly(BAMPC) networks were studied for the first time, and promising physical and mechanical properties are reported.

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