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VB 2019 HEM No Layer High Energy Materials O2N NO2 N N N N N3 N N N NO2 NO O2N 2 NO O2N 2 NO O2N 2 O2N NO2 Vlad Bacauanu MacMillan Research Group Group Meeting July 25th, 2019 What Are High Energy Materials? compound that stores chemical energy high energy material and which upon stimulation undergoes (HEM) rapid decomposition with release of energy and gas explosives propellants pyrotechnics Applications of High Energy Materials The obvious – military applications Civil and scientific applications mining civil engineering oil industry space exploration High Energy Materials – Outline Generals aspects of high energy materials Very brief history Fundamental properties Decomposition via deflagration or detonation Primary vs secondary explosives Oxygen balance Synthesis of high energy materials Safety precautions in HEM labs Explosophore functional groups Examples of synthetic approaches Recent avenues within the field Nitrogen-rich molecules Strained energetic materials: HNIW and ONC Exploring stereochemistry of materials Book References for High Energy Materials High Energy Materials Chemistry of High-Energy Materials Organic Chemistry of Explosives Jai P. Agrawal Thomas M. Klapötke Jai P. Agrawal & Robert D. Hodgson 1st ed. (2010) 4th ed. (2017) 1st ed. (2007) History of Development of High Energy Materials 1943 CH3 O2N NO2 gunpowder N N O2N NO2 (KNO3 + C + S) N N 1863 1880 TNT O NO 1894 O2N NO2 2 HMX ONO2 NO2 O2NO ONO2 O2NO ONO2 PETN nitroglycerin ONO2 800 1000 1850 1900 1950 present OH O N NO 2 N N 2 1855 O2N NO2 O N 2 N N NO2 ONO 2 picric O2NO 1885 1930’s N N O acid O N NO O NO 2 CL-20 2 2 O2N NO2 N N ONO 1987 2 n RDX nitrocellulose 1867 N dynamite NO2 in Radical Chemistry, 1st ed.;, C., Wiley-VCH: Weinheim, Germany, 2004. Fundamental Properties of High Energy Materials ΔHf heat of formation (ΔHf) C + H2 + N2 + O2 explosive Q heat of explosion (Q) explosive explosion products (CO2, CO, H2O, N2, etc.) density of material (ρ) volume of gases released (V) velocity of detonation (VOD) detonation pressure (DP) speed with which detonation wave propagates peak pressure in detonation wave explosive power = Q x V brisance ~ ρ x VOD2 “ability of explosive to do useful work” shattering power of an explosive specific impulse (Isp) sensitivity total impulse delivered by a unit of propellant to heat, shock, friction, electrical discharge, etc. Deflagration vs. Detonation in High Energy Materials deflagration to detonation transition Deflagration – propellants (always for explosives; Detonation – explosives very rapid burning avoid for propellants) extremely rapid decomposition subsonic propagation wave supersonic propagation wave controlled, regular process uncontrollable past initiation Deflagration vs. Detonation in High Energy Materials Detonation – explosives extremely rapid decomposition supersonic propagation wave uncontrollable past initiation how does a detonation wave propagate? hot gases high pressure material is material material decomposes released shock front compressed heats up with release of gas Classification of High Energy Materials OH Primary Secondary (high) Hg(CNO)2 Pb(N3)2 explosives explosives O2N NO2 NO K+ 2 very sensitive to stimuli relatively insensitive N NO2 N N N N rapid detonation high performance O2N NO2 N N N N N N inititate decomposition of main load of N + 2º explosive or propellant explosive ensemble N N O2N K O2N NO2 Classification of High Energy Materials OH Primary Secondary (high) Hg(CNO)2 Pb(N3)2 explosives explosives O2N NO2 NO K+ 2 very sensitive to stimuli relatively insensitive N NO2 N N N N rapid detonation high performance O2N NO2 N N N N N N inititate decomposition of main load of N + 2º explosive or propellant explosive ensemble N N O2N K O2N NO2 Traditional Approach To Explosives Design Me H O CO O2N NO2 C H + O + N 2 2 N2 combustable fuel oxidant (neither) exothermic NO2 products an explosive is a mixture of fuel and oxidant – balancing the two is ideal Ω oxygen balance for generic CaHbNcOd (d – 2a – b/2) x 1600 Ω = ΩCO2 = M (d – a – b/2) x 1600 ΩCO = M Importance of Having Good Oxygen Balance for Secondary Explosives How is oxygen balance important? Me O2N NO2 explosion 1 CO2 1 H2O + + 1.5 N2 3 CO 3 C 1.5 H2 Ω = –74% NO2 enthalpy of formation incomplete oxidation of C,H backbone ΔHf,CO2 << ΔHf,CO < ΔHf,C = 0 wasted potential energy of the fuel ΔHf,H2O < ΔHf,H2 = 0 Ideal explosion for TNT How do I fix my bad OB? Me Me O2NO O2N NO2 5.25 O 2 O2N NO2 + + O2NO ONO2 oxidizer deficit ONO NO2 2 NO2 bad Ω good Ω issues overcome by formulation 7 CO2 + 2.5 H2O + 1.5 N2 with others HEMs Most Commonly Used Explosives in Military Me O N NO O2N NO2 2 2 O2N NO2 N N N N N N N NO 2 O2N NO2 NO2 TNT RDX HMX trinitrotoluene (1880) research department explosive (1930’s) high melting explosive (1943) stable, cheap, melt-castable stable, more expensive, very powerful next generation high-performance explosive? organic synthesis! Safety Precautions for High Energy Materials Safety precautions in HEM labs first synthesis on 250 mg scale or less keep distance from experiments (tongs, clamps) protective equipment must be used z protective gloves Kevlar wrist protectors full-visor face shield ear protectors protective leather or Kevlar jacket Student in the Klapötke group Safety is not a joke – refusing to follow the safety guidelines gets you fired! Kemsley, J. Chem. Eng. News 2008, 86, 22 Explosophores – Common Functional Groups in HEM V. Plets’ theory of explosophores (1953) –– several common functional groups in explosives nitro, nitrate, and nitroso azo and azide O O N N N N N N N N O O O O N-haloamino chlorate and perchlorate F Cl O O N N Cl Cl O O O O F Cl O fulminates peroxide and ozonide metal acetylides O O O C C M C N O O O M Kemsley, J. Chem. Eng. News 2008, 86, 22 Synthesis of Nitrate Esters and Nitramines Direct nitration of alcohols HO O O2N NO + source HO OH 2 O O O2N NO2 OH O O N alcohol substrate 2 conc. HNO N2O5 100% HNO 3 NO BF 3 2 4 N – w/ conc. H2SO4 + – BF4 [NO2] [NO3] NO2 Direct nitration of amines F3C CF3 F3C CF3 Me HNO3 Me H H 100% HNO3 O2N NO2 ZnCl N N N N 2 NH N NO2 N TFAA N Ac2O HO O2NO NO2 NO2 acidic conditions work best for non-basic amines proceeds via N-chloro intermediate (from AcOCl) Synthesis of Nitrate Esters and Nitramines Tertiary amides undergo nitrolysis readily to form nitramines Ac Ac O N NO O 2 2 nitrolysis N N N N O N2O5 NO2 N R N HO R N N N N HNO3 Ac Ac O2N NO2 N-alkyl bonds can also undergo nitrolysis to form nitramine products O N NO O N NO N 2 2 2 2 HNO3, NH4NO3 N N N N N N N N Ac2O N N NO 2 O2N NO2 Nitrosation followed by oxidation or exchange nitration is also a viable strategy O N NO + ON NO + 2 2 HN NH NO N N NO2 N N N N N H or [O] NO NO2 Synthesis of Aromatic and Aliphatic C–NO2 Compounds Aromatic C–NO2 products Cl Cl NH2 O N NO O N NO H2SO4, HNO3 2 2 NH3 2 2 Cl Cl 150 ºC Cl Cl toluene, 150 ºC H2N NH2 NO2 NO2 electrophilic aromatic substitution is a staple subsequent SNAr is facile and enabling Aliphatic C–NO2 products + – NH3 Cl NO2 DMDO oxidation of amines – + + – with various reagents Cl H3N NH3 Cl acetone O2N NO2 – + Cl H3N O2N O2N NO2 O O H NO2 O2N NO2 additions of nitro nucleophiles aq. MeOH O2N NO2 O2N NO2 Synthesis of Nitrogen-Rich Compounds for HEM Development Cl Cl NH2 cyanogen azide for tetrazole synthesis N N N N N N Cl N Cl Cl Cl NH2 Cl H2N N N 1) SNAr, DMF, 90 ºC N3 CN N SNAr is H2N 2) H2SO4, HNO3 N widely employed Na+ H2N 3) NH3, acetone N N N N N N N SNAr NH 2 N NH O2N NO2 2 N N H2N NH NH2 HNO3 N H N O2N O2N NO2 2 N N N N N HN N N NH2 N H O2N NH N N O N NO NO 2 2 2 N N N N N N N NH2 N H2N NH2 HN NO N 2 N N NO2 Design of Novel Energetic Materials Higher performance materials increased heat of explosion maximize energy of material higher detonation pressure (per unit volume) higher detonation velocity Oxidation of C,H backbone Inherent strain Nitrogen-rich molecules N N Me N O N NO N 2 N 2 N N N N O2N NO2 O N NO N 2 N N 2 N N H2N NH N N 2 H2N NH2 NO2 O2N NO2 N N H H energy from “combustion” strain release – extra energy energy from formation of N2 traditional approach newer approach newer approach Nitrogen-Rich Molecules as High Energy Materials Nitrogen-rich molecules BDEs normalized by bond order N N N N N N N N N=N N N N N N N good performance (Q, VOD, P) candidates for “green” HEM N-rich propellants lead to less erosion very endothermic compounds (ΔHf >> 0) N N N N N N N N N R N N N R R R stable relatively stable too unstable not endothermic enough high energy high energy Klapötke, T.
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