Synthesis and Characterization of 1,4‐Dimethyl‐5‐Aminotetrazolium 5‐Nitrotetrazolate

1,4‐Dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate ( 2 ) was synthesized in high yield from 1,4‐dimethyl‐5‐aminotetrazolium iodide ( 1 ) and silver 5‐nitrotetrazolate. Both new compounds ( 1, 2 ) were characterized using vibrational (IR and Raman) and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁴N, ¹⁵N), elemental analysis and single crystal X‐ray diffraction. 1,4‐Dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate ( 2 ) represents the first example of an energetic material which contains both a tetrazole based cation and anion. Compound 2 is hydrolytically stable with a high melting point of 190 °C (decomposition). The impact sensitivity of compound 2 is very low (30 J), it is not sensitive towards friction (>360 N). The molecular structure of 1,4‐dimethyl‐5‐aminotetrazolium iodide ( 1 ) in the crystalline state was determined by X‐ray crystallography: orthorhombic, F_ddd, a=1.3718(1) nm, b=1.4486(1) nm, c=1.6281(1) nm, V=3.2354(5) nm³, Z=16, ρ=1.979 g cm⁻¹, R₁=0.0169 (F>4σ(F)), wR₂ (all data)=0.0352.     

Combustion Mechanism of Consolidated Mixtures of 5‐amino‐1H‐tetrazole with Potassium Nitrate or Sodium Nitrate

Recently, 5‐amino‐1H‐tetrazole is developed for practical use as a substitute for sodium azide, which is conventionally used as a fuel component of gas generating agents for automobile airbags. In this study, the combustion mechanisms of the mixtures 5‐amino‐1H‐tetrazole/potassium nitrate and 5‐amino‐1H‐tetrazole/sodium nitrate have been examined. It has been found that the Granular Diffusion Flame model is applicable to the tested samples even when a molten layer exists at the burning surface. In addition, it is shown that within the pressure range of 1–5 MPa, the greatest factor which affects the burning rate is the diffusion process. It is also demonstrated that the fuel component decomposes first, and the oxidizer decomposes next. Meanwhile, it has also been confirmed that the burning rate increases with an increase in pressure because the flame approaches the burning surface and the amount of heat transfer to the solid phase increases. In spite of a decrease in the amount of heat transfer from the gas phase to the solid phase and an increase in the thickness of the condensed phase reaction zone for a mixture with higher fuel content, there are little differences in the burning rates probably because of an increase in the rate of decomposition of the solid phase.     

Synthesis and Characterization of 3,4,5‐Triamino‐1,2,4‐Triazolium 5‐Nitrotetrazolate

3,4,5‐Triamino‐1,2,4‐triazolium 5‐nitrotetrazolate ( 2 ) was synthesized in high yield from 3,4,5‐triamino‐1,2,4‐triazole (guanazine) ( 1 ) and ammonium 5‐nitrotetrazolate. The new compound 2 was characterized by vibrational (IR and Raman) and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁵N), elemental analysis and single crystal X‐ray diffraction (triclinic, P(‐1), a=0.7194(5), b=0.8215(5), c=0.8668(5) nm, α=75.307(5), β=70.054(5), γ=68.104(5)°, V=0.4421(5) nm³, Z=2, ϱ=1.722 g cm⁻¹, R₁=0.0519 [F>4σ(F)], wR₂(all data)=0.1154). The ¹⁵N NMR spectrum and X‐ray crystal structure (triclinic, P‐1, a=0.5578(5), b=0.6166(5), c=0.7395(5) nm, α=114.485(5)°, β=90.810(5)°, γ=97.846(5)°, V=0.2286(3) nm³, Z=2, ϱ=1.658 g cm⁻¹, R₁=0.0460 [F>4σ(F)], wR₂(all data)=0.1153) of 1 were also determined.     

Crystal Structure and Improved Synthesis of 1‐(2H‐Tetrazol‐5‐yl)guanidium Nitrate

Energetic derivatives of tetrazoles are one of the key areas of research focus in pursuit of novel high energy materials, useful as propellants and explosives. Herein, the crystal structure and an improved synthetic procedure of 1‐(2H‐tetrazol‐5‐yl)guanidine ( 1 ) and its nitrate salt ( 2 ) are reported. The compounds were structurally characterized by spectroscopic (FT‐IR, ¹H NMR, ¹³C NMR) and elemental analysis. The molecular structure of tetrazolyl guanidium nitrate ( 2 ) was solved using low temperature single‐crystal X‐ray diffraction. 2 crystallized as its hemihydrate in the orthorhombic space group Fdd2, with a crystal density of 1.69 g cm⁻³. Thermal behavior and decomposition of the molecules were studied with differential scanning calorimetry (DSC). Molar enthalpy of formation (Δ_fH^m) of compound 2 was back calculated from heat of combustion (Δ_cH⁰) value obtained experimentally using bomb calorimetric measurements. Lattice enthalpy of 1‐(2H‐tetrazol‐5‐yl)guanidium nitrate was directly calculated from measured crystal density using Jenkins equation. Preliminary ballistic parameters of the compound were predicted and compared with reported high nitrogen tetrazole derivatives.     

Experimental and Theoretical Study of 1,5‐Diamino‐4‐H‐1,2,3,4‐Tetrazolium Perchlorate

The synthesis and characterization of 1,5‐diamino‐1,2,3,4‐tetrazolium perchlorate were carried out. Experimental evidence strongly supports the protonation of a nitrogen atom of the tetrazole ring, including the structure observed in a single crystal X‐ray diffraction study of the title compound. Quantum chemical calculations were performed at the CCSD(T)/6‐311G(2df, p)//MP2/6‐311G(d, p) level of theory to determine the relative energies of all possible N‐protonated structures of the 1,5‐diamino‐1,2,3,4‐tetrazole ring. The predicted geometry of the most stable isomer compares favorably with the experimentally observed structure.     

Synthesis and Characterization of 1‐Azido‐2‐Nitro‐2‐Azapropane and 1‐Nitrotetrazolato‐2‐Nitro‐2‐Azapropane

1‐Azido‐2‐nitro‐2‐azapropane ( 1 ) was synthesized in high yield from 1‐chloro‐2‐nitro‐2‐azapropane and sodium azide. 1‐Nitrotetrazolato‐2‐nitro‐2‐azapropane ( 2 ) was synthesized in high yield from 1‐chloro‐2‐nitro‐2‐azapropane and silver nitrotetrazolate. The highly energetic new compounds ( 1 and 2 ) were characterized using vibrational (IR and Raman) and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁴N), elemental analysis and low‐temperature single crystal X‐ray diffraction. 1‐Azido‐2‐nitro‐2‐azapropane ( 1 ) represents a covalently bound liquid energetic material which contains both a nitramine unit and an azide group in the molecule. 1‐Nitrotetrazolato‐2‐nitro‐2‐azapropane ( 2 ) is a covalently bound room‐temperature stable solid which contains a nitramine group and a nitrotetrazolate ring unit in the molecule. Compounds 1 and 2 are hydrolytically stable at ambient conditions. The impact sensitivity of compound 1 is very high (<1 J) whereas compound 2 is less sensitive (<6 J).     

Hot‐Wire Ignition of AN‐Based Emulsions

Emulsions based on ammonium nitrate (AN) and water locally ignited by a heat source do not undergo sustained combustion when the pressure is lower than some threshold value usually called the Minimum Burning Pressure (MBP). This concept is now being used by some manufacturers as a basis of safety. However, before a technique to reliably measure MBP values can be designed, one must have a better understanding of the ignition mechanism. Clearly, this is required to avoid under ignitions which could lead to the erroneous interpretation of failures to ignite as failures to propagate. In the present work, facilities to prepare and characterize emulsions were implemented at the Canadian Explosives Research Laboratory. A calibrated hot‐wire ignition system operated in a high‐pressure vessel was also built. The system was used to study the ignition characteristics of five emulsion formulations as a function of pressure and ignition source current. It was found that these mixtures exhibit complicated pre‐ignition stages and that the appearance of endotherms when the pressure is lowered below some threshold value correlates with the MBP. Thermal conductivity measurements using this hot‐wire system are also reported.     

Synthesis and Energetic Properties of 4,4′,5,5′‐Tetranitro‐2,2′‐biimidazolate(N4BIM) Salts

This paper describes the synthesis and characterization of several salts of 4,4′,5,5′‐tetranitro‐2,2′‐biimidazolate (N4BIM). Each of the salts were characterized chemically, thermally, morphologically, as well as with respect to destructive stimuli (impact, electrostatic discharge, friction, thermal). These salts show promise as propellant ingredient additives, and in particular, the bis‐triaminoguanidinium salt of N4BIM displays excellent burn rate and combustion behavior. Our combustion studies have shown that TAGN4BIM displays a fast burning rate and has the lowest pressure dependence exponent yet measured for a triaminoguanidinium salt.     

4,5‐Bis(5‐tetrazolyl)‐1,2,3‐triazole: Synthesis and Performance

4,5‐Bis(5‐tetrazolyl)‐1,2,3‐triazole (BTT) was synthesized by a new method. Its structure was characterized by IR and ¹³C NMR spectroscopy and elemental analysis (EA). The thermal stability of BTT was investigated by TG‐DSC technique. The kinetic parameters including activation energy and pro‐exponential factor were calculated by Kissinger equation. The combustion heat, detonation products, hygroscopicity, impact, and friction sensitivity were also measured. The formation heat, detonation pressure, and detonation velocity of BTT were calculated. BTT has high detonation pressure and detonation velocity (P=35.36 GPa, D=8.971 km s⁻¹). BTT has potential application prospect as environmentally friendly gas generant, insensitive explosive and solid propellant.     

Synthesis of functionalizable and biodegradable polymers via ring‐opening polymerization of 5‐benzyloxy‐trimethylene carbonate and ε‐caprolactone

The biomedical applications of poly(ε‐caprolactone) (PCL) were limited for its high hydrophobicity and crystallinity. In this study, we copolymerized CL with amorphous 5‐hydroxyl‐trimethylene carbonate (HTMC) to solve the problem. The 5‐benzyloxy‐trimethylene carbonate (BTMC) was synthesized to copolymerize with CL, then hydrogenolyzed to obtain hydroxyl pendant groups. A serial of copolymers with different BTMC molar ratio were synthesized and their chemical structures and thermal properties were thoroughly studied with NMR, FT‐IR, GPC, XRD, DSC, and TGA. Finally we examined the water contact angle of the copolymers. DSC and XRD results showed that the PCL segments in the copolymers crystallized below 16.8%. BTMC molar content and the crystallinity of the copolymers increased after hydrolysis. With the introduced hydroxyl pendant groups, the deprotected copolymers improved their hydrophilic property significantly, and the copolymer with 9.3% HTMC molar content had static water contact angle as low as 36.5°. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and Energetic Properties of Bis‐(Triaminoguanidinium) 3,3′‐Dinitro‐5,5′‐Azo‐1,2,4‐Triazolate (TAGDNAT): A New High‐Nitrogen Material

This paper describes the synthesis and characterization of bis‐(triaminoguanidinium)‐3,3′‐dinitro‐5,5′‐azo‐1,2,4‐triazolate (TAGDNAT), a novel high‐nitrogen molecule that derives its energy release from both a high heat of formation and intramolecular oxidation reactions. TAGDNAT shows promise as a propellant or explosive ingredient not only due to its high nitrogen content (66.35 wt.‐%) but also due to its high hydrogen content (4.34 wt.‐%). This new molecule has been characterized with respect to its morphology, sensitivity properties, explosive, and combustion performance. The heat of formation of TAGDNAT was also experimentally determined. The results of these studies show that TAGDNAT has one of the fastest low‐pressure burning rates (at 6.9 MPa) measured till date, 6.79 cm s⁻¹ at 6.9 MPa (39% faster than triaminoguanidinium azotetrazolate (TAGzT), a comparable high‐nitrogen/high‐hydrogen material). Furthermore, its pressure sensitivity is 0.507, a 33% reduction compared to TAGzT.     

The Development of a New Synthesis Process for 3,3′‐Diamino‐4,4′‐azoxyfurazan (DAAF)

Process optimization studies were performed for the preparation of the high explosive 3,3′‐diamino‐4,4′‐azoxyfurazan (DAAF). These process studies were pursued to address issues such as problematic waste generation products, particle size, impurities, and manufacturability. This paper describes the original synthesis method and inherent issues. An optimization process was designed to investigate the issues with purity and manufacturability. Particle size effects were addressed by adding a recrystallization step to the synthesis. Ultimately, a complete solution to all observed issues was found with a new synthesis process, which now allows DAAF to be prepared without any impurities, with good particle size and without the need for recrystallization. Importantly, the new synthesis process can be performed in an environmentally friendly manner, with the production of non‐hazardous waste.     

Quantitative Determination of ε‐phase in polymorphic HNIW using X‐ray Diffraction Patterns

An X‐ray diffraction method was applied for the quantitative determination of the ε‐Hexanitrohexaazaisowurtzitane (HNIW) in polymorphs of HNIW. The XRD patterns of four polymorphs illustrate the unique nonoverlapping peak at 19.9° which belongs to ε‐HNIW. The intensity ratio of the peak at 19.9° of ε‐HNIW to the peak at 79.6° of α‐Al₂O₃ is proportional to the weight ratio of standard ε‐HNIW to the internal standard of α‐Al₂O₃, which enables the internal standard method. When the particle size of the sample is less than 10 μm, the content of ε‐HNIW ranging from 70 to 100 wt.‐% can be determined with an absolute error below 2.0%.     

Influence of Physical Characteristics and Ingredients on the Minimum Burning Pressure of Ammonium Nitrate Emulsions

It has been well established that sustained combustion in ammonium nitrate water‐based emulsions (AWEs) can only occur if the ambient pressure is held above some threshold value, usually referred to as the ‘minimum burning pressure’ (MBP). For the commercial explosives industry, a good knowledge of the MBP for particular AWE formulations is essential to estimate safe operating pressures for the associated manufacturing and handling processes. In these processes, AWE products are most often pumped in closed systems and at elevated temperature. While previous studies have established that the MBP can depend critically on major ingredients, its dependence on physical characteristics such as temperature and viscosity had never been investigated. Moreover, the consequences of alterations in measurement methodologies on the resulting measured MBP values had not been studied.     

Synthesis and biological activity of medium molecular weight polymers containing 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl‐5‐fluorouracil

A new monomer, 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl‐5‐fluorouracil (ETBFU), was synthesized by reaction of 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl chloride and 5‐fluorouracil. The homopolymer of ETBFU and its copolymers with acrylic acid (AA) or vinyl acetate (VAc) were prepared by photopolymerization using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETBFU and its polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The ETBFU content in poly(ETBFU‐co‐AA) and poly(ETBFU‐co‐VAc) was 43 and 14 mol%, respectively. The apparent number‐average molecular weight (M_n) of the polymers determined by GPC ranged from 8400 to 11 300. The in vitro cytotoxicity of the samples against mouse mammary carcinoma (FM3A), mouse leukaemia (P388), and human histiocytic lymphoma (U937) cancer cell lines decreased in the order 5‐FU ≥ ETBFU > poly(ETBFU) > poly(ETBFU‐co‐AA) > poly(ETBFU‐co‐VAc). The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐fluorouracil at all doses tested. © 2000 Society of Chemical Industry     

Synthesis and characterization of a random terpolymer of L‐lactide, ϵ‐caprolactone and glycolide

A random terpolymer of L ‐lactide (LL), ?‐caprolactone (CL) and glycolide (G) has been synthesized in bulk at 130 °C using stannous octoate as the coordination–insertion initiator. The terpolymer, poly(LL‐ran‐CL‐ran‐G), has been characterized by a combination of analytical techniques: GPC, ¹H NMR, ¹³C NMR, DSC and TG. Molecular weight characterization by GPC shows a unimodal molecular weight distribution with values of M _n = 1.01 × 10⁵ g mol^?1 and M _w / M _n = 2.17. Compositional and microstructural analysis by ¹H NMR and ¹³C NMR, respectively, reveal a terpolymer composition of LL:CL:G = 74:15:11 (mol%) with a chain microstructure consistent with random monomer sequencing. This latter view is supported by the terpolymer temperature transitions (T_g and T_m) from DSC and the thermal decomposition profile from TG. The results and, in particular, the conclusion that it is a random rather than a statistical terpolymer are discussed in the light of current theories regarding the mechanism of this type of polymerization. © 2001 Society of Chemical Industry     

X‐Ray reflectivity study of polyimide thin films swollen by 1,3‐butadiene and n‐butane

X‐ray reflectivity measurements were performed on two different polyimide thin films synthesized from 2,2‐bis(3,4‐carboxyphenyl)hexafluoropropane dianhydride (6FDA) in 1,3‐butadiene and n‐butane. In 1,3‐butadiene at 2.3 atm, the film thickness increased by 24–30%. However, the film thickness increased by only 10% in n‐butane at 2.3 atm. Excessive increases in film thickness were shown in 1,3‐butadiene, but the decreases in film density were minor. The probability of the condensation of 1,3‐butadiene in the films is indicated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1818–1825, 2000     

The High‐Pressure Characterization of Energetic Materials: 1,4‐Dimethyl‐5‐Aminotetrazolium 5‐Nitrotetrazolate

In‐situ high‐pressure room temperature synchrotron X‐ray diffraction and infrared microspectroscopy were used to examine the structural and vibrational properties and the equation of state of 1,4‐dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate (DMATNT). The X‐ray measurements show a smoothly varying pressure‐volume relationship to 20 GPa. However, the anisotropic ratios of the unit cell parameters reveal a discontinuity near 3.3 GPa, which can be attributed to an irreversible isostructural phase transition. A significant increase in the Infrared spectral intensity near this pressure coupled with Dayvdov splitting of the NO₂ bending and scissoring modes suggest the transition results in a skewing of the NO₂ groups and increasing asymmetry of the hydrogen bonding sublattice.     

An Energetic N‐Oxide and N‐Amino Heterocycle and its Transformation to 1,2,3,4‐Tetrazine‐1‐oxide

This study reports the preparation of 1‐amino‐1,2,3‐triazole‐3‐oxide (DPX2) and its transformation to 1,2,3,4‐tetrazine‐1‐oxide. DPX‐2 provides insight into a novel N‐oxide/N‐amino high‐nitrogen system, being the first energetic material in this class. The ability of this material to undergo a nitrene insertion forming 1,2,3,4‐tetrazine‐1‐oxide was also studied, and evidence for this material, the first non‐benzoannulated 1,2,3,4‐tetrazine‐1‐oxide, is presented. The existence of both of these materials opens new strategies in energetic materials design. DPX2 was characterized chemically (Infrared, Raman, NMR, X‐ray) and as a high explosive in terms of energetic performances (detonation velocity, pressure, etc.) and sensitivities (impact, friction, electrostatic). DPX‐2 was found to possess good thermal stability and moderate sensitivities, indicating the viability of N‐amino N‐oxides as a strategy for the preparation of new energetic materials.     

Synthesis and biological activity of phthalimide‐based polymers containing 5‐fluorouracil

The attachment of anticancer agents to polymers is a promising approach towards reducing the toxic side‐effects and retaining the potent antitumour activity of these agents. A new tetrahydrophthalimido monomer containing 5‐fluorouracil (ETPFU) and its homopolymer and copolymers with acrylic acid (AA) and with vinyl acetate (VAc) have been synthesized and spectroscopically characterized. The ETPFU contents in poly(ETPFU‐co‐AA) and poly(ETPFU‐co‐VAc) obtained by elemental analysis were 21 mol% and 20 mol%, respectively. The average molecular weights of the polymers determined by gel permeation chromatography were as follows: M_n = 8900 g mol^?1, M_w = 13 300 g mol^?1, M_w/M_n = 1.5 for poly(ETPFU); M_n = 13 500 g mol^?1, M_w = 16 600 g mol^?1, M_w/M_n = 1.2 for poly(ETPFU‐co‐AA); M_n = 8300 g mol^?1, M_w = 11 600 g mol^?1, M_w/M_n = 1.4 poly(ETPFU‐co‐VAc). The in vitro cytotoxicity of the compounds against FM3A and U937 cancer cell lines increased in the following order: ETPFU > 5‐FU > poly(ETPFU) > poly(ETPFU‐co‐AA) > poly(ETPFU‐co‐VAc). The in vivo antitumour activities of all the polymers in Balb/C mice bearing the sarcoma 180 tumour cell line were greater than those of 5‐FU and monomer at the highest dose (800 mg kg^?1). © 2002 Society of Chemical Industry