US EPA

7687639 

Journal Article 

"CLEAN NITRATIONS USING DINITROGEN PENTOXIDE (N2O5)-A UK PERSPECTIVE" [1] 

Millar, RW; Colclough, ME; Arber, AW; Claridge, RP; Endsor, RM; Hamid, J; , 

2010 

NOVA SCIENCE PUBLISHERS, INC 

HAUPPAUGE 

ENERGETIC MATERIALS: CHEMISTRY, HAZARDS AND ENVIRONMENTAL ASPECTS 

77-+ 

WOS:000281545700003 

Dinitrogen pentoxide (N2O5) is a nitrating agent which is receiving increasing interest worldwide on account of the cleanliness of its nitration reactions and the potential of such reactions to offer environmentally-friendly processes for the manufacture of energetic materials - explosives and propellants. A review of this chemistry is timely, the subject having been comprehensively reviewed in 1997, and focuses on work carried out in the United Kingdom in furthering the exploitation of N2O5 nitrations.In particular, the following topics are covered:N2O5 ring-opening nitrations (synthesis of di-/polynitrate esters and nitramine-nitrates)-reviewed/updatedN2O5 selective nitrations (for energetic polymer precursor synthesis) reviewed/updatedOther N2O5 nitrations (e.g. C-nitro compounds) reviewed/updatedNitrodesilylation reactions (synthesis of nitrate esters and nitramines)Nitrations on solid supports using N2O5 (clays, zeolites and related materials)Nitrations in alternative solvent systems using N2O5 (perfluorocarbons and perfluoroethers)Regioselective nitration of toluene and clean nitration of dinitrotoluenes using N2O5 (for environmentally-friendly process for TNT manufacture)Processes for the scale-up of N2O5 production and the economics of these processes.Some of the above processes are under consideration for the commercial manufacture of explosives, e.g. the toluene nitration processes would eliminate the production of redwater in the manufacture of TNT and are of interest to the US Department of Defense. Many of the other processes are of fundamental importance as they offer novel and clean routes either for the synthesis of the functionalities (C-nitro, nitrate ester, nitramine) which are incorporated into energetic materials, or in some cases actual energetic molecules themselves (e.g. hexanitrofluorene, diglycerol tetranitrate, "Tris-X" - a polynitramine). An additional important product class is nitrate esters of strained-ring molecules (epoxides and oxetanes) for the synthesis of energetic polymer precursors (polyNIMMO and polyGlyN). The process economics for using N2O5 in scaled-up reactions are also discussed.This chapter is in the nature of a review of the use of N2O5 as an environmentally-friendly nitrating agent and brings the coverage of this topic up to date. It should be of interest to workers in the field of energetic materials synthesis who require a timely survey of this topic. 

Howell, JR; Fletcher, TE; 

978-1-60876-267-5