Chemical Kinetics and Heat Transfer Issues for a Safe Bench Scale Production of Partially Triazole Substituted Glycidyl Azide Polymer (GAP)

Dubois, Charles; Désilets, S.; Nadeau, Gaston; Gagnon, Nicole

doi:10.1002/prep.200390016

Cited by 12 publications

(9 citation statements)

References 10 publications

(9 reference statements)

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“…Due to the spontaneous and highly exothermic nature of this cycloaddition reaction, the study of the reaction kinetics between GAP and each curing agent is a safety necessity that must be undertaken before any multigram-scale reaction is attempted to eliminate the risk of runaway reactions and possible ignition of the energetic mixture [6].…”

Section: Introductionmentioning

confidence: 99%

Investigations on Non‐isocyanate Based Reticulation of Glycidyl Azide Pre‐polymers

Araya‐Marchena

St‐Charles

Dubois

2019

Propellants Explo Pyrotec

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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.

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Section: Introductionmentioning

confidence: 99%

Investigations on Non‐isocyanate Based Reticulation of Glycidyl Azide Pre‐polymers

Araya‐Marchena

St‐Charles

Dubois

2019

Propellants Explo Pyrotec

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“…The preparation of branched, hydroxyl‐telechelic GAP by combined degradation (chain cleavage) and azidation of high molecular weight polyepichlorohydrin has been studied extensively by Ahad and co‐workers in Canada during the late 1980s and early 1990s 23. Instead of using such customized GAP, linear GAP diol can be branched to virtually any desired degree of functionalization with propargyl alcohol through azide‐alkyne thermal cycloaddition 24. Interestingly, such propargyl alcohol branched GAP seems only to have been investigated as a means of tailoring the burning rate behavior and not as a tool for improving the mechanical characteristics of cured GAP.…”

Section: Resultsmentioning

confidence: 99%

Curing of Glycidyl Azide Polymer (GAP) Diol Using Isocyanate, Isocyanate‐Free, Synchronous Dual, and Sequential Dual Curing Systems

Hagen

Jensen

Unneberg

et al. 2014

Propellants Explo Pyrotec

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a] 1I ntroductionIn solid propellant rocketry,p ropulsion units in fielded and currently operational missile systems are founded upon ar elatively small number of firmly established propellant technologies, most of which have an extensive historical track record. While propulsion systems with either limited or no restrictions with respect to exhaust plume signature have their basis in ammonium perchlorate (AP) composites with inert binder systems (preferably aluminized), smokeless systems are based on nitrate ester plasticized binders (nitrocellulose, polyethers, polyesters) with or without nitramine filler materials [1].C ombination of the two sorts gives rise to the high-performance propellant types important in domains such as submarine-launched ballistic missiles, applications where performance with regards to specific impulse is particularly critical [2].Although implemented propellant technology has now remained somewhat static for ac onsiderable period of time, new incentives have accelerated the development of new generations of solid rocket propellants. Increasingly stringent legislature associated with the handling and use of many chemical species traditionally used in rocket propellant formulations (heavy metal compounds, perchlorates, isocyanates), when assessed in conjuncture with at ightening export bureaucracy and the diminishing production base for many important raw materials (a result of plant closures and industry consolidation during recent decades), have all contributed to an increased willingness by relevant manufacturers to evaluate new propellant candidates.The bulk of contemporary research efforts directed towards new solid rocket propellant candidates is concentrated around new energetic binder systems and chlorine-free filler materials, as well as associated formulation additives (curing agents, bonding agents, burning rate modifiers) [3-Abstract:G lycidyl azide polymer (GAP) is an important energetic binder candidate for new minimum signature solid composite rocket propellants, but the mechanical properties of such GAP propellants are often limited. The mechanical characteristics of composite rocket propellants are mainly determined by the nature of the binder system and the binder-filler interactions. In this work, we report ad etailed investigation into curing systems for GAP diol with the objective of attaining the best possible mechanical characteristics as evaluated by uniaxial tensile testing of non-plasticized polymer specimens. We started out by investigating isocyanate and isocyanate-free curing systems, the latter by using the crystalline and easily soluble alkyne curing agent bispropargylhydroquinone (BPHQ). In the course of the presented study,w et hen assessed the feasi-bility of dual curing systems, either by using BPHQ and isophorone diisocyanate (IPDI) simultaneously (synchronous dual curing), or by applying propargyl alcohol and IPDI consecutively (sequential dual curing). The latter method, which employs propargyl alcohol as ar eadily available and adjustable hydroxyl...

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“…They observed a higher burning rate at relatively lower pressure for triazole substituted GAPs. They described a safe production route with lower molecular weight GAP plasticizer and suggested the use of propargyl alcohol and a semibatch reactor to avoid sudden temperature raise in the reaction mixture 38 .…”

Section: Copolymers and Other Derivatives Of Gapmentioning

confidence: 99%

Untitled

2017

Org. Commun.

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:In preparation of energetic composite formulations, functionally terminated pre-polymers have been used as binder. After physically mixing the pre-polymers with oxidizing components, metallic fuel, burning rate modifier and other minor ingredients, they are cured with a suitable curing agent to provide physical and chemical stability. These pre-polymers could be functionalized with carboxyl, epoxide or hydroxyl groups at varying average chain functionalities. For carboxyl-terminated pre-polymers, an epoxy functional curing agents could be used. If the prepolymer possesses hydroxyl groups, isocyanate functional curing agents are the most suitable curing agents in terms of easy and efficient processing. Glycidyl azide polymer (GAP) is one of the well-known low-molecular weight energetic liquid pre-polymer, which was developed to use as energetic binder, high performance additive and gas generator for high performance smokeless composite propellant and explosive formulations. Linear or branched GAP can be synthesized by nucleophilic substitution reaction of corresponding poly(epichlorohydrin) (PECH) with sodium azide through replacement of chloromethyl groups of PECH with pendant energetic azido-methyl groups on the polyether main chain. Positive heat of formation (+957 kJ/kg) enables exothermic and rapid decomposition of GAP producing fuel rich gases. Its polyether main chain provides GAP with relatively low glass transition temperature o C) and presence of hydroxyl functional groups allows it to have easy processing in curing with isocyanate curing agents to form covalently crosslinked polyurethane structure. These outstanding properties of GAP enable it to be used as energetic polymeric binder and high performance additive in preparation of energetic materials and low vulnerable explosives.

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Chemical Kinetics and Heat Transfer Issues for a Safe Bench Scale Production of Partially Triazole Substituted Glycidyl Azide Polymer (GAP)

Cited by 12 publications

References 10 publications

Investigations on Non‐isocyanate Based Reticulation of Glycidyl Azide Pre‐polymers

Investigations on Non‐isocyanate Based Reticulation of Glycidyl Azide Pre‐polymers

Curing of Glycidyl Azide Polymer (GAP) Diol Using Isocyanate, Isocyanate‐Free, Synchronous Dual, and Sequential Dual Curing Systems

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