Reactive Energetic Plasticizers for Energetic Polyurethane Binders Prepared via Simultaneous Huisgen Azide-Alkyne Cycloaddition and Polyurethane Reaction

Reactive energetic plasticizers (REPs) for use in glycidyl azido polymer (GAP) based polyurethane (PU) energetic binders were investigated. These REPs consisted of an activated terminal alkyne group that was expected to give rise to Huisgen azide‐alkyne 1,3‐dipolar cycloaddition within the specific pot life for a PU formulation to prevent the migration of plasticizers, and with a gem‐dinitro group as an energy resource. A quantitative miscibility investigation between the plasticizers and uncured GAP showed that REPs exhibited better miscibility than conventional energetic plasticizers. The plasticization effect of the REPs on the GAP prepolymer with respect to the reduction of the viscosity illustrated REPs can effectively reduce the viscosity of the GAP prepolymer from 6,015 cP to 150–240 cP at the processing temperature when 50 wt‐% of REP was added. A comparison of the click reactivity and activation energies (Ea) of REPs and GAP prepolymer elucidated that the reactivity of azide‐alkyne cycloaddition depended on the dipolarophilicity of REPs which could be controlled by adjusting the length of methylene spacer between electron‐withdrawing groups (EWG) and neighboring alkynes in REPs. Thermogravimetric analysis manifested REP/GAP‐based PU binders maintained the thermal stability of the control GAP‐based PU binder. The mechanical properties and impact insensitivity of the GAP‐based PU binders were also improved by the incorporation of REPs.