Effects of Additives on ε‐HNIW Crystal Morphology and Impact Sensitivity

Crystals of γ‐HNIW were transformed into crystals of ε‐HNIW by application of a drowning‐out process in the presence of different additives, namely ethylene glycol, triacetin, and aminoacetic acid. They show different effects on the crystal morphology of ε‐HNIW and cause less angular and more regular structures. Investigation of the sensitivities of the different ε‐HNIW crystals shows that their angles and regularity have an influence on the impact sensitivity. Aminoacetic acid selectively inhibits the growth of individual ε‐HNIW crystal faces to modify the morphology into spherical shape, these ε‐HNIW crystals are of much lower sensitivity, even compared with general RDX and HMX explosives.     

Energetic Salts of 5‐(5‐Azido‐1H‐1,2,4‐triazol‐3‐yl)tetrazole

Several metal and nitrogen‐rich salts of the recently presented 5‐(5‐azido‐1H‐1,2,4‐triazol‐3‐yl)tetrazole (AzTT), including silver ( 1 ), copper(I) ( 2 ), potassium ( 3 ), cesium ( 4 ), copper(II) ( 7 ), ammonium ( 8 ), and guanidinium ( 9 ), as well as the respective double‐salts of 3 , 4 , 8 and 9 , were prepared and well characterized by IR and multinuclear (¹H, ¹³C, ¹⁴N) NMR spectroscopy, DSC, mass spectrometry, elemental analysis and one ( 4 ) additionally by single‐crystal X‐ray diffraction. The sensitivities towards impact, friction and electrostatic discharge were determined according to BAM standards, revealing most of the metal salts as highly sensitive and the nitrogen‐rich salts as insensitive. The metal salts were further tested for their ability of being primary explosives.     

Thermal and Sensitivity Study of Dihydroxyl Ammonium 5,5′‐Bistetrazole‐1,1′‐diolate (TKX‐50)‐based Melt Cast Explosive Formulations

Dihydroxyl ammonium 5,5′‐bistetrazole‐1,1′‐diolate (TKX‐50) is a promising energetic material with predicted performance similar to RDX as well as to CL‐20. In the present study, TKX‐50 was evaluated as a possible replacement for RDX in TNT‐based, aluminized as well as non‐aluminized melt cast formulations. Thermal analysis reveals the compatibility of TKX‐50 with benchmark explosives like RDX and TNT in explosive formulations. This paper describes the thermal and sensitivity study of TKX‐50 with RDX and TNT‐based melt cast explosives. The result indicated that TKX‐50 can be effectively used as a RDX replacement in melt cast explosive formulations. TKX‐50/TNT‐based aluminized composition shows more thermal stability than RDX/TNT based composition, which clearly indicated the usefulness of TKX‐50 in melt cast explosive formulations.     

Acid–base behavior of an oligomer of 3‐amino‐1,2,4‐triazole

We report the acid–base behavior of OATA, an oligomer synthesized from 3‐amino‐1,2,4‐triazole (ATA). We analyze the UV–vis spectroscopy at different media, and we analyze and discuss the acid–base equilibria taking into account tautomeric equilibria at different pH. The low aqueous solubility at neutral pH can be attributed to the neutral form. Indeed, OATA was synthesized in an ordinary filter paper, which can be used as a sensor for ammonia as well as endpoint indication. Using the OATA‐containing paper, ammonia concentrations in a solution as low as 5 ppm could be measured. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermomechanical properties and shape memory effect of epoxidized natural rubber crosslinked by 3‐amino‐1,2,4‐triazole

A thermally induced shape memory polymer based on epoxidized natural rubber (ENR) was produced by curing the ENR with 3‐amino‐1,2,4‐triazole as a crosslinker in the presence of bisphenol‐A as a catalyst. Dynamic mechanical and tensile analysis was conducted to examine the variation of glass transition temperature, stiffness, and extensibility of the vulcanizates with the amount of curatives. Shape memory properties of the ENR vulcanizates were characterized by shape retention and shape recovery. It was revealed that the glass transition temperature of the ENR vulcanizates could be tuned well above room temperature by increasing the amount of curing agents. Also, ENR vulcanizates with T_g higher than ambient temperature showed good shape memory effects under 100% elongation, and the response temperatures of the recovery were well matched with T_g of the samples. Copyright © 2006 Society of Chemical Industry     

Preparation of supramolecular thermally repairable elastomer by crosslinking of maleated polyethylene‐octene elastomer with 3‐amino‐1,2,4‐triazole

A supramolecular thermally repairable elastomer was prepared by crosslinking of semicrystalline maleated polyethylene‐octene elastomer (mPOE) with 3‐amino‐1,2,4‐triazole (ATA) via melt mixing method. Crosslinking of mPOE with ATA induced supramolecular hydrogen bonding networks; the nature of the networks was affected by the amount of ATA, which was confirmed by Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. In addition, at 3 phr ATA content or above, a small number of ionic domains were observed in the tan δ curves of dynamic mechanical analysis. Dynamic mechanical analysis also showed that the storage modulus increased with increasing ATA content along with increase in the relaxation transition temperature which revealed strengthening of the network structures. Differential scanning calorimetry showed a reduction in melting temperature and degree of crystallinity of the mPOE with increasing ATA content which is attributed to hydrogen bonding networks. The shape memory property of the mPOE matrix imparted a thermal healing capability which was greatly enhanced in the presence of hydrogen bonding networks. The scratch marked on the polymer surface healed within 20 s after being heated at around 80 °C. © 2014 Society of Chemical Industry     

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.     

Supramolecular thermoplastic elastomer with thermally scratch repairable effect from 3‐amino‐1,2,4‐triazole crosslinked maleated polyethylene‐octene elastomer/nylon 12 blends

In this study, nylon 12 (5–25 wt %) was melt blended with a supramolecular thermally repairable thermoplastic elastomer (ATA‐POE), which was generated by crosslinking of maleated polyethylene‐octene elastomer (mPOE) with 3‐amino‐1,2,4‐triazole (ATA), in an internal mixer. The effect of nylon 12 content on the phase morphology, thermomechanical properties, and thermally triggered scratch repairing effects of the ATA‐POE/nylon 12 blends was investigated. Scanning electron microscopy results showed that nylon 12 formed a dispersed phase with submicron scale in a continuous ATA‐POE phase. Fourier transform infrared spectroscopy and differential scanning calorimetry analysis revealed that there are extensive hydrogen bonding interactions between the ATA‐POE and nylon 12 in the blends, which was manifested by a decrease in the melting temperature of each polymer component. Tensile and dynamic mechanical test showed that tensile modulus increased with increasing nylon 12 contents in the blend with maintaining fairly high elastic recoverability. Furthermore, the blends containing up to 20 wt % of nylon 12 showed good scratch repairing effects when they are heated above melting temperature of the ATA‐POE phase in the blend. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41511.     

Enantioselective Addition of Diphenylphosphine to 3‐Methyl‐4‐nitro‐5‐alkenylisoxazoles

An enantioselective Michael addition reaction of diphenylphosphine to substituted alkenylisoxazoles has been developed. The reaction proceeds efficiently under mild conditions with high yields (up to 99%) and moderate to excellent enantioselectivities (up to 92%) thus providing a hitherto unavailable direct access to a library of chiral tertiary phosphine‐functionalized isoxazoles.     

Synthesis and application of cotton‐based chelate fibers grafted with poly(1‐vinyl‐1,2,4‐triazole) side chains

Cotton‐based chelate fibers grafted with poly(1‐vinyl‐1,2,4‐triazole) (PVTAZ) side chains were synthesized facilely by ozone‐induced graft polymerization of 1‐vinyl‐1,2,4‐triazole (VTAZ) monomer onto cotton fibers. The synthesis conditions were optimized to improve the yield and mechanical strength of the products. The obtained cotton‐g‐PVTAZ fibers were characterized and evaluated for batch adsorption of heavy metal ions from aqueous solutions. The maximum adsorption capacity of Ag(I), Pb(II), and Cu(II) on the fibers at pH 6.8 was 522, 330, and 184 mg/g, respectively. At 30% graft yield, the Young's modulus of cotton fiber increased about 26.5%, and its adsorption capacities of Ag(I), Pb(II), and Cu(II) increased about 2.6, 1.9, and 1.4 times, respectively. After washed with 0.1 mol/L HNO₃ solutions, the adsorbed metal ions were eluted, and the regenerated cotton‐g‐PVTAZ fibers could be used repeatedly for water treatment. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41617.     

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 ω‐amino‐α‐phenylcarbonate alkanes and their polymerization to [n]‐polyurethanes

Aliphatic [n]‐polyurethanes have recently been synthesized from ω‐isocyanato‐α‐alkanols or, more traditionally, by cationic ring‐opening polymerization of cyclourethanes or by the Bu₂Sn(OMe)₂‐promoted polycondensation of ω‐hydroxy‐α‐O‐phenylurethane alkanes. For the latter procedures, the conditions employed do not seem to be suitable for highly functionalized monomers. In contrast, the polymerization of ω‐amino‐α‐phenylcarbonate alkanes is expected to occur under milder conditions. ω‐Amino‐α‐phenylcarbonate alkanes have been synthesized from 6‐aminohexanol (1) and 3‐aminopropanol (6). The procedure involves the N‐Boc protection of the amino group, followed by activation of the alcohol. Removal of the N‐Boc affords the corresponding ω‐amino‐1‐O‐phenyloxycarbonyloxyalkane hydrochlorides. Other oligomeric comonomers between 1 and 6 have been prepared. The polymerization of these precursors takes place in the absence of metal catalysts to afford the corresponding linear and regioregular [n]‐polyurethanes. The procedure described is useful for the preparation of stable ω‐amino‐α‐phenylcarbonate alkane derivatives, which possess varied chain lengths between the terminal functions. These monomers yield [n]‐polyurethanes having various structures starting from just two aminoalkanols. The polyurethanes were obtained in high yields, with reasonable molecular weight and polydispersity values, and they were characterized spectroscopically and thermally. These studies reveal constitutionally uniform structures that are free of carbonate or urea linkages. Copyright © 2010 Society of Chemical Industry     

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.     

Structural and Preliminary Explosive Property Characterizations of New 3,4,5‐Triamino‐1,2,4‐triazolium (Guanazinium) Salts

Two new highly stable energetic salts were synthesized in reasonable yield by using the high nitrogen‐content heterocycle 3,4,5‐triamino‐1,2,4‐triazole and resulting in its picrate and azotetrazolate salts. 3,4,5‐Triamino‐1,2,4‐triazolium picrate (1) and bis(3,4,5‐triamino‐1,2,4‐triazolium) 5,5′‐azotetrazolate (2) were characterized analytically and spectroscopically. X‐ray diffraction studies revealed that protonation takes place on the nitrogen N1 (crystallographically labelled as N2). The sensitivity of the compounds to shock and friction was also determined by standard BAM tests revealing a low sensitivity for both. B3LYP/6–31G(d, p) density functional (DFT) calculations were carried out to determine the enthalpy of combustion (Δ_cH (1) =−3737.8 kJ mol⁻¹, Δ_cH (2) =−4577.8 kJ mol⁻¹) and the standard enthalpy of formation (Δ_fH° (1) =−498.3 kJ mol⁻¹, (Δ_fH° (2) =+524.2 kJ mol⁻¹). The detonation pressures (P (1) =189×10⁸ Pa, P (2) =199×10⁸ Pa) and detonation velocities (D (1) =7015 m s⁻¹, D (2) =7683 m s⁻¹) were calculated using the program EXPLO5.     

Synthesis and characterization of poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) copolymer beads for heavy‐metal removal

We prepared poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [poly(EGDMA–VTAZ)] beads (average diameter = 150–200 μm) by copolymerizing ethylene glycol dimethacrylate (EGDMA) with 1‐vinyl‐1,2,4‐triazole (VTAZ). The copolymer composition was characterized by elemental analysis and found to contain five EGDMA monomer units for each VTAZ monomer unit. The poly(EGDMA–VTAZ) beads had a specific surface area of 65.8 m²/g. Poly(EGDMA–VTAZ) beads were characterized by Fourier transform infrared spectroscopy, elemental analysis, surface area measurements, swelling studies, and scanning electron microscopy. Poly(EGDMA–VTAZ) beads with a swelling ratio of 84% were used for the heavy‐metal removal studies. The adsorption capacities of the beads for Cd(II), Hg(II), and Pb(II) were investigated in aqueous media containing different amounts of these ions (5–750 mg/L) and at different pH values (3.0–7.0). The maximum adsorption capacities of the poly(EGDMA–VTAZ) beads were 85.7 mg/g (0.76 mmol/g) for Cd(II), 134.9 mg/g (0.65 mmol/g) for Pb(II), and 186.5 mg/g (0.93 mmol/g) for Hg(II). The affinity order toward triazole groups on a molar basis was observed as follows: Hg(II) > Cd(II) > Pb(II). pH significantly affected the adsorption capacity of the VTAZ‐incorporated beads. The equilibrium data were well fitted to the Redlich–Peterson isotherm. Consideration of the kinetic data suggested that chemisorption processes could have been the rate‐limiting step in the adsorption process. Regeneration of the chelating‐beads was easily performed with 0.1M HNO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4276–4283, 2006     

Synthesis and Energetic Properties of Imidazolium and 2‐Methylimidazolium Salts of 3‐Nitro‐1,2,4‐Triazol‐5‐One

Two new energetic salts of 3‐nitro‐1,2,4‐triazol‐5‐one (NTO) were described. Imidazole and 2‐methylimidazole salt of NTO decomposes exothermically at 217 and 258 °C respectively. Detonation parameters calculated for 2‐methylimidazole salt are significantly smaller than that of 2,4,6‐trinitrotoluene (TNT) but these parameters estimated for imidazole salt are comparable with that of TNT. Structure of new compounds were investigated with NMR and IR spectroscopy. Impact and friction sensitivity determined for new compounds are smaller than for pure NTO, so they are more safe during handling.     

Synthesis and characterization of novel polyimides derived from 2‐amino‐5‐(4‐aminophenyl)‐thiazole

A new kind of aromatic unsymmetrical diamine monomer containing thiazole ring, 2‐amino‐5‐(4‐aminophenyl)‐thiazole (AAPT), was synthesized. A series of novel polyimides were prepared by polycondensation of AAPT with various aromatic dianhydrides by one‐step polyimidation process. The synthesized polyimides had inherent viscosity values of 0.36–0.69 dL/g and were easily dissolved in highly dipolar solvents. Meanwhile, strong and flexible polyimide films were obtained, which have good thermal and thermo‐oxidative stability with the glass transition temperatures (T_g) of 276.7–346.1°C, the temperature at 5% weight loss of 451–492°C in nitrogen and 422–440°C in air, as well as have outstanding mechanical properties with the tensile strengths of 94–122 MPa, elongations at breakage of 5–18%. These films also had dielectric constants of 3.12–3.38 at 10 MHz. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,extraction, and anti‐bacterial studies of some new bis‐1,2,4‐triazole derivatives part I

A series of new bis triazole Schiff base derivatives (4) were prepared in good yields by treatment of 4‐amino‐3,5‐diphenyl‐4H‐1,2,4‐triazole (3) with bisaldehydes (1). Schiff bases (4) were reduced with NaBH₄ to afford the corresponding bisaminotriazoles (5). All the new compounds were characterized by IR, ¹H NMR and ¹³C NMR spectral data. Their overall extraction (log K_ex) constants for 1 : 1 (M : L) complexes and CHCl₃/H₂O systems were determined at 25 ± 0.1°C to investigate the relationship between structure and selectivity toward various metal cations. The extraction equilibrium constants were estimated using CHCl₃/H₂O membrane transfer with inductively coupled plasma‐atomic emission spectroscopy spectroscopy. The stability sequence of the triazole derivatives in CHCl₃ for the metal cations was exhibited a characteristic preference order of extractability to metal ions [Fe(III) > Cu(II) > Pb(II) > Co(II) > Ni(II) > Mn(II) > Zn(II) > Mg(II) > Ca(II)]. The compounds were tested for anti‐microbial activity applying agar diffusion technique for 11 bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,chemical, and thermoelectric properties of n‐type π‐conjugated polymer composed of 1,2,4‐triazole and pyridine rings and its metal complexes

A soluble n‐type π‐conjugated polymer ( polymer 1 ) composed of a 1,2,4‐triazole ring substituted by a 4‐n‐octylphenyl subunit at the 4‐position of the 1,2,4‐triazole ring and pyridine‐2,5‐diyl rings was synthesized by Ni(cod)₂ (cod = 1,5‐cyclooctadiene) promoted dehalogenation polycondensation of 3,5‐bis(2‐bromopyridyl)‐4‐n‐octylphenyl‐1,2,4‐triazole ( monomer 1 ). A polymer complex ( polymer‐BiCl₃ ) was synthesized by the reaction of polymer 1 with BiCl₃. The UV–vis spectrum of polymer 1 exhibited an absorption maximum (λ_max value) at a longer wavelength than that exhibited by monomer 1 revealing that its π‐conjugation system was expanded along the polymer chain. Polymer 1 was electrochemically active in film, and the electrochemical reaction was accompanied with electrochromism. Thermoelectoric properties of polymer 1 and polymer‐BiCl₃ were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39928.