Energetic Nitrogen‐Rich Polymers with a Tetrazene‐Based Backbone

Abstract

New energetic polymers were synthesized from monomers containing a trans-2-tetrazene unit. In contrast to traditional binders, such as inert hydroxytelechelic polybutadiene or glycidyl azide polymers-in which the energetic features are on the side chains-the energetic groups in the polytetrazenes are incorporated directly in the polymer backbone. Thermal analyses demonstrated that decomposition occurs at approximately 130 8C, regardless of the polymer structure. Glass-transition temperatures ranged from À34.2 to 0.2 8C and could be lowered further (to À61 8C) with the help of a new diazidotetrazene energetic plasticizer. Interestingly, hexafluoroisopropanol (HFIP) enabled complete, room-temperature depolymerization within 1 week. This depolymerization should enable the recycling of unused pyrotechnic compositions based on these new binders.

A review: Multidimensional internal plasticization of molecular structure in energetic polymer

“…Proverbially, the flexibility of energetic polymer is obstructed by bulky and polar energetic groups, bringing about the decline of mechanical properties. [1][2][3][4][5][6][7][8][9][10][11] To eliminate the defect, plasticizers are traditionally blended to interact physically with polymers, thus improving their flexibility, rheology, and processability. However, highly plasticized propellants may suffer from the migration of plasticizers, which may bring about poor aging behavior or severe safety concern.…”

“…Proverbially, the flexibility of energetic polymer is obstructed by bulky and polar energetic groups, bringing about the decline of mechanical properties 1–11 . To eliminate the defect, plasticizers are traditionally blended to interact physically with polymers, thus improving their flexibility, rheology, and processability.…”

(2‐Vinyltetrazolyl)furoxans as New Potential Energetic Monomers

“…[7,8] Energetic polymers and binders bearing various explosophoric groups such as nitric esters, tetrazoles or azides have been synthesized. [9,10] Recently, novel high-performance tetrazene- [11] and tetrazine-based [12] energetic polymers were prepared. So far, commonly used polymers are nitrocellulose, azidocellulose nitrate or glycidyl azide polymer (GAP).…”

Translation of a Phosphine- and Azide-Based Reaction to Chemical Modification of Biomolecules in Ionic Liquid

“…16 Although unsubstituted tetrazenes are thermally unstable at room temperature, 17 tetraalkyl-substituted tetrazene compounds are known to be stable even at temperatures higher than 100 °C (Scheme 2 A). 18 19 On the other hand, aryltetrazenes decompose relatively easily, 20 paralleling the well-known higher reactivity/lower stability of arylazide compounds compared to alkylazide groups. 21 Reactions of amine derivatives and azide compounds have been developed for some systems including the interconversion of ammonium azide salts to the parent tetrazene under high pressure 22 as well as nucleophilic attack of a metal amide group to organic azides to generate unstable tetrazene intermediates (Scheme 2 B).…”