Synthesis and Characterization of Reactive Energetic Plasticizers for Poly(glycidyl azide-co-tetramethylene glycol)-Based Polyurethane Binders

Two reactive energetic plasticizers, 3-((2,2-dinitropropoxy)methoxy)prop-1-yne and 4-((2,2-dinitropropoxy)methoxy)but-1-yne which can react with an azido-containing poly(glycidyl azide-co-tetramethylene glycol) prepolymer by cupper-free 1,3-dipolor cycloaddition (“Click”) reaction, were synthesized and characterized, in order to investigate their plasticizing performance and catalyst-free 1,3-dipolar cycloaddition reactivity on energetic polyurethane binders. Two reactive energetic plasticizers showed better plasticizing performance than commercial energetic plasticizers. In the reactivity point of view, 3-((2,2-dinitropropoxy)methoxy)prop-1-yne exhibited higher Click reactivity than 4-((2,2-dinitropropoxy)methoxy)but-1-yne. Two synthesized plasticizers were found to fulfill the requirements for use as reactive energetic plasticizers.

Compatibility of energetic plasticizers with the triblock copolymer of polypropylene glycol-glycidyl azide polymer-polypropylene glycol (PPG-GAP-PPG)

Glycidyl azide polymer (GAP) is well known as an energetic prepolymer, but its application as a binder in propellants is limited due to its relatively high glass transition temperature and relatively poor mechanical properties. Copolymerization of GAP with polypropylene glycol (PPG) has been shown to improve GAPs properties because of the good thermal and mechanical properties of PPG. In this research we synthesized triblock copolymer of PPG-GAP-PPG and the compatibilities of this copolymer were investigated with energetic plasticizers (20% w/w) n-butyl nitroxyethylnitramine (BuNENA), trimethylolethane trinitrate (TMETN), and butanetriol trinitrate (BTTN) by solubility parameter, differential scanning calorimetry (DSC), rheological analysis, scanning electron microscopy (SEM) and vacuum stability test (VST). The DSC results showed that BuNENA had better compatibility with the triblock copolymer in comparison to TMETN and BTTN. It reduced the Tg of PPG-GAP-PPG from −58 to −63 °C. The rheological analysis was in good agreement with the DSC results obtained for the compatibility of the plasticizers. In the case of the addition of 20% w/w BuNENA, the viscosity of copolymer/plasticizer decreased from 550 to 128 mPa s, indicating appropriate compatibility of plasticizer with the copolymer. SEM images showed a better distribution of BuNENA in the copolymer matrix.