Preparation and thermal reactivity of hydrazinium 2,n-pyridinedicarboxylates (n=3, 4, 5 and 6)

Hydrazinium 2,n-pyridinedicarboxylates of general compositions N₂H₅HA, (N₂H₅)₂A·H₂O and N₂H₅HA·H₂A, where H ₂ A=2,n-pyridinedicarboxylic acid (n=3, quinolinic acid;n=4, lutidinic acid; n=5, isocinchomeronic acid and n=6, dipicolinic acid) have been prepared by the neutralisation of aqueous solution of hydrazine hydrate with the respective acids, in stoichiometric ratios. Formation of these hydrazinium derivatives has been confirmed by analytical, IR spectral and thermal studies. Among these, the monohydrazinium salts are anhydrous whereas the dihydrazinium salts are monohydrated. While lutidinic and dipicolinic acids form all the three types of salts, the quinolinic and isocinchomeronic acids do not form N₂H₅HA·H₂A and N₂H₅HA, respectively, except the other two types. Infrared spectra of these salts reveal N-N stretching frequencies of the hydrazinium ion in the region 970-950 cm^-1. The simultaneous TG and DTA of these salts show that all of them decompose without clear melting and lose hydrazine endothermically between 200 and 280°C, except dihydrazinium isocinchomeronate monohydrate in which half of the hydrazine molecule is lost exothermically, to give pyridinemono- or dicarboxylic acid intermediate which further decomposes exothermically to gaseous products. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preparation, spectral and thermal studies of pyrazinecarboxylic acids and their hydrazinium salts

Some new hydrazinium 2-pyrazinecarboxylate and 2,3-pyrazinedi-carboxylate salts of the formulae N₂H₅pc, N₂H₅pc.H₂O (Hpc = 2-pyrazinecarboxylic acid), N₂H₅Hpdc, (N₂H₅)₂pdc.H₂O and N₂H₅(Hpdc).H₂pdc (H₂pdc = 2,3-pyrazinedi-carboxylic acid) have been prepared by neutralization of aqueous hydrazine hydrate with the respective acids in appropriate molar ratios. The free acids and their hydrazinium salts have been characterized by analytical, IR spectroscopic and thermal studies. IR spectra of all the salts show N-N stretching frequencies of the N₂H₅ ⁺ ion in the region 975–960 cm^-1. The thermoanalytical behaviour of the free acids and their salts has been investigated by simultaneous TG and DTA. While pyrazinecarboxylic acid shows single-step endothermic (229°C) complete decomposition, pyrazindi-carboxylic acid shows exothermic decarboxylation followed by identical endothermic decomposition as that of the former. Similarly, salts of the monocarboxylic acid show endothermic effects during pyrolysis, whereas salts of the dicarboxylic acid show endothermic followed by exothermic decomposition. The acids and their salts both undergo complete decomposition to gaseous products.     

Synthesis and anhydrous proton conductivity of poly(5-vinyltetrazole) prepared by free radical polymerization

5-Vinyltetrazole (VT)-based polymer is mainly produced by ‘click chemistry’ from polyacrylonitrile due to the unavailability of 5-vinyltetrazole monomer, which usually produces copolymers of VT and acrylonitrile rather than pure poly(5-vinyltetrazole) (PVT). In present work, VT was synthesized from 5-(2-chloroethyl)tetrazole via dehydrochlorination. A series of PVT with different molecular weight were synthesized by normal free radical polymerization. The chemical structures of VT and PVT were characterized by ¹H NMR and FTIR. PVT without any doped acid exhibits certain proton conductivity at higher temperature and anhydrous state. The proton conductivity of PVT decreases at least 2 orders of magnitude after methylation of tetrazole. PVT and PVT/H₃PO₄ composite membranes are thermally stable up to 200 °C. The glass transition temperature (T_g) of PVT/xH₃PO₄ composite membranes is shifted from 90 °C for x = 0.5 to 55 °C for x = 1. The temperature dependence of DC conductivity for pure PVT exhibits a simple Arrhenius behavior in the temperature range of 90–160 °C, while PVT/xH₃PO₄ composite membranes with higher H₃PO₄ concentration can be fitted by Vogel–Tamman–Fulcher (VTF) equation. PVT/1.0H₃PO₄ exhibits an anhydrous proton conductivity of 3.05 × 10⁻³ at 110 °C. The transmission of the PVT/xH₃PO₄ composite membrane is above 85% in the wavelength of visible light and changes little with acid contents. Thus, PVT/xH₃PO₄ composite membranes have potential applications not only in intermediate temperature fuel cells but also in solid electrochromic device.     

Synthesis and decarboxylation of N-acyl-α-triphenylphosphonio-α-amino acids: a new synthesis of α-(N-acylamino)alkyltriphenylphosphonium salts

4-Phosphoranylidene-5(4H)-oxazolones 1 undergo hydrolysis in THF in the presence of HBF₄ at room temperature to give N-acyl-α-triphenylphosphonioglycines 3 (R² = H) in very good yields. 4-Alkyl-4-triphenylphosphonio-5(4H)-oxazolones 2 react with water in CH₂Cl₂/THF solution without any acidic catalyst at 0-5 °C in a few days yielding N-acyl-α-triphenylphosphonio-α-amino acids 3 (R² = Me) or α-(N-acylamino)alkyltriphenylphosphonium salt 4 (R² = CH₂OMe). α-Triphenylphosphonio-α-amino acids 3, on heating up to 105-115 °C under reduced pressure (5 mmHg) or on treatment with diisopropylethylamine in CH₂Cl₂ at 20 °C undergo decarboxylation to give the corresponding α-(N-acylamino)alkyltriphenylphosphonium salts 4, usually in very good yields.     

Microwave-assisted synthesis of 2-aminonicotinic acids by reacting 2-chloronicotinic acid with amines

2-(Methylamino)nicotinic acid was readily prepared in high yield by reacting 2-chloronicotinic acid with 40% aq MeNH₂ under microwave irradiation either at 120 °C for 2 h or at 140 °C for 1.5 h. Subsequently, we found that a range of 2-aminonicotinic acids could be obtained under microwave heating. The optimal reaction conditions involved the use of 3 equiv of amine, water as the solvent and heating at 200 °C for 2 h in the presence of diisopropylethylamine (3 equiv).     

Amperometric detection of hydrazine by cyclic voltammetry and flow injection analysis using ruthenium modified glassy carbon electrodes

Glassy carbon electrodes modified with (5-amino-1,10-phenanthroline)bis(bipyridine)ruthium(II) chloride hydrate, [(bpy)₂Ru(5-phenNH₂)]Cl₂·H₂O, are shown to oxidize hydrazine with excellent sensitivity. The presence of an amine group on the ruthenium complex facilitates electropolymerization onto the electrode surface. Using cyclic voltammetry, a large catalytic current is observed upon oxidation of hydrazine in phosphate buffer (pH 5.0), compared to the current obtained from the ruthenium-modified electrode with no hydrazine present. The sensitivity of cyclic voltammetry is sufficient for obtaining a linear calibration curve for hydrazine over the range of 10⁻⁵ to 10⁻² M. Hydrodynamic amperometry was used to determine the working potential for flow injection analysis. The limit of detection for hydrazine was determined to be 8.5 μM using FIA. The thickness of these films was shown to increase linearly with the number of electropolymerization cycles, in the range of 1000-2500 nm for 5-20 cycles, respectively, using Rutherford backscattering spectrometry (RBS). RBS analysis also suggests that the film is multilayered with the outermost layers containing a high ruthenium concentration, followed by layers where the concentration of ruthenium decreases linearly and approaches zero at the electrode surface.     

Synthesis and physico-chemical properties of copoly(ester-sulfonates) of 1,1-bis (3-methyl-4-hydroxy phenyl) cyclohexane with 2,4-toluene disulfonyl and terephthaloyl chlorides

Copoly(ester-sulfonates) of varying compositions have been synthesized by interfacial polycondensation technique by using H₂O-CHCl₃ as an interphase, alkali as an acid acceptor and sodium lauryl sulfate-cetyl trimethyl ammonium bromide as mixed emulsifiers at 0 °C for 4 h. Copolymers are characterized by IR and NMR spectral data, viscosity in three different solvents at three temperatures and little solvent and temperature effect is found on [η]; and density (1.3430-1.3406 g/cm³) by floatation method. Copolymers possess excellent solubility in common solvents and chemical resistance against water, acids, alkalis and salts. They possess moderate to good tensile strength (10.6-79.5 N/mm²), excellent volume resistivity (7.5-28 × 10¹⁶ Ω cm), electric strength (53-118 kV/mm) and dielectric constant (1.3-1.58). They are thermally stable up to about 349-373 °C in an N₂ atmosphere and possess high T_g (136-196 °C). DTA endo/exothermic transitions supported either decomposition or formation of new product(s). Physical properties of copolymers are improved with increasing terephthlate content.     

Hydrazinium Oxydiacetates and Oxydiacetate Dianion Complexes of Some Divalent Metals with Hydrazine

Hydrazinium oxydiacetate salts of formulae N₂H₅(Hoda)⋅H₂oda, N₂H₅(Hoda) and (N₂H₅)₂oda (H₂oda=oxydiacetic acid) and complexes of the types, M(oda)⋅2N₂H₄⋅xH₂O (where M=Co, Ni and Cd; x=0 for Co and Ni;x=1 for Cd) and Zn(oda)⋅N₂H₄⋅H₂O have been prepared and characterized by analytical, spectral, thermal and X-ray powder diffraction data. IR data document the existence of N₂H⁺ ₅ ion in the simple salts and the bidentate coordination of both hydrazine and dianion in the complexes. Complete decomposition of hydrazinium salts takes place via oxydiacetic acid intermediate. Cobalt and nickel complexes decompose in a single step, whereas zinc and cadmium complexes decompose through hydrazinate intermediates. However, all the metal complexes yield metal oxide as the final residue. Isomorphic nature of the cobalt and nickel complexes is evident from XRD data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Low-temperature heat capacity and thermodynamic properties of crystalline carboxin (C12H13NO2S)

Carboxin was synthesized and its heat capacities were measured with an automated adiabatic calorimeter over the temperature range from 79 to 380 K. The melting point, molar enthalpy (Δ_fusH_m) and entropy (Δ_fusS_m) of fusion of this compound were determined to be 365.29±0.06 K, 28.193±0.09 kJ mol⁻¹ and 77.180±0.02 J mol⁻¹ K⁻¹, respectively. The purity of the compound was determined to be 99.55 mol% by using the fractional melting technique. The thermodynamic functions relative to the reference temperature (298.15 K) were calculated based on the heat capacity measurements in the temperature range between 80 and 360 K. The thermal stability of the compound was further investigated by differential scanning calorimetry (DSC) and thermogravimetric (TG) analysis. The DSC curve indicates that the sample starts to decompose at ca. 290 °C with the peak temperature at 292.7 °C. The TG-DTG results demonstrate the maximum mass loss rate occurs at 293 °C corresponding to the maximum decomposition rate.     

Preparation and characterization of proton-conducting sulfonated poly(ether ether ketone)/phosphatoantimonic acid composite membranes

The solid proton conductor, phosphatoantimonic acid, HSbP₂O₈ · H₂O was prepared by ion exchange of the corresponding potassium salt. The composite membranes of SPEEK with up to 40 wt% of HSbP₂O₈ · H₂O were prepared by introducing the solid proton conductor from the aqueous suspension. The composite membranes were characterized using FT-IR, powder X-ray diffraction, SEM, DSC/TGA. Thermal stability of the composite membranes was slightly lower than that of SPEEK. The composite membranes had higher water uptake when compared with SPEEK and the membranes exhibited controlled swelling up to 50 °C. The proton conductivity of the membranes was measured under 100% relative humidity up to 70 °C. The composite membranes showed enhanced proton conductivity up to 20 wt% of HSbP₂O₈ · H₂O and the conductivity was reduced with further increase of HSbP₂O₈ · H₂O loading. A maximum of four-fold increase in proton conductivity at 70 °C was observed for the composite membrane with 20 wt% of solid proton conductor.     

A novel polybenzimidazole-modified gold electrode for the analytical determination of hydrogen peroxide

The imine of polybenzimidazole (PBI) is chemically oxidized by hydrogen peroxide (H₂O₂) in the presence of acetic acid (AcOH). Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopies (XPS) showed that when the AcOH concentration remained constant, the degree of oxidation increased with increasing H₂O₂ levels. Moreover, the imine also exhibited electrochemical redox behavior. Based on these properties, a PBI-modified Au (PBI/Au) electrode was developed as an enzyme-free H₂O₂ sensor. At an applied potential of −0.5 V vs. Ag/AgCl, the current response of the PBI/Au electrode was linear with H₂O₂ concentration over a range from 0.075 to 1.5 mM, with a sensitivity of 55.0 μA mM⁻¹ cm⁻². The probe had excellent stability, with <5% variation from its initial response current after storage at 50 °C for 10 days. Potentially interfering species such as ascorbic or uric acid had no effect on sensitivity. Sensitivity improved dramatically when multiwalled carbon nanotubes (MWCNT) were incorporated in the probe. Under optimal conditions, the detection of H₂O₂ using a MWCNT-PBI/Au electrode was linear from 1.56 μM to 2.5 mM, with a sensitivity of 928.6 μA mM⁻¹ cm⁻². Analysis of H₂O₂ concentrations in urine samples using a MWCNT-PBI/Au electrode produced accurate real-time results comparable to those of traditional HPLC methods.     

Two highly proton-conductive molecular hybrids based on ionized water clusters and poly-Keggin-anion chains

Two proton-conductive molecular hybrid complexes, {[Zn(H₂O)₈][H(H₂O)₂](HINO)₄(PMo₁₂O₄₀)}_n (1) and {[Mn(H₂O)₈][H(H₂O)_2.5](HINO)₄(PMo₁₂O₄₀)}_n (2), were constructed by introducing protonated water clusters, transition metal ionized water clusters and [PMo₁₂O₄₀]³⁻ anions in the gallery of H-bonding networks based on isonicotinic acid N-oxide (HINO). Single-crystal X-ray diffraction analyses at 293 K revealed that both complexes presented exactly the same three-dimensional (3D) hydrogen-bonded networks with large one-dimensional (1D) channels. Interestingly, [PMo₁₂O₄₀]³⁻ anions just filled in the 1D channels and self-assembled into poly-Keggin-anion chains. Thermogravimetric analyses both show no weight loss in the temperature range of 20-100 °C, indicating that all water molecules in the unit structure are not easily lost below 100 °C. Surprisingly, the proton conductivities of 1 and 2 in the temperature range of 85-100 °C under 98% RH conditions reached high proton conductivities of 10⁻³ S cm⁻¹. A possible mechanism of the proton conduction was proposed according to the experimental results.     

Reaction of perfluoro-1-ethylindan with SiO2/SbF5 and skeletal transformations of perfluoro-3-ethylindan-1-one under the action of SbF5 and SiO2/SbF5

Perfluoro-1-ethylindan heated with excess of SiO₂ in an SbF₅ medium at 75 °C and then treated with water, gives 4-carboxy-perfluoro-3-methylisochromen-1-one. Perfluoro-3-ethylindan-1-one is converted, under the action of SbF₅ at 70 °C, to perfluoro-2-(but-2-en-2-yl)benzoic acid as a mixture of E- and Z-isomers. When the reaction temperature is raised to 125 °C, a solution of salts of perfluoro-3,4-dimethyl-1H-isochromen-1-yl and perfluoro-4-ethyl-1H-isochromen-1-yl cations is obtained. Increase in the reaction time lowers the content of a salt of the latter cation in the solution. Hydrolysis of the solution of the salts gives perfluoro-3,4-dimethylisochromen-1-one and perfluoro-4-ethylisochromen-1-one.     

Synthesis and properties of soluble and light-colored poly(amide-imide-imide)s based on tetraimide-dicarboxylic acid (TIDA) and various aromatic diamines: TIDA from 4,4′-oxydiphthalic anhydride, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, and 3-aminobenzoic acid

A new tetraimide-dicarboxylic acid (TIDA) I was synthesized starting from 3-aminobenzoic acid (m-ABA), 4,4′-oxydiphthalic anhydride (ODPA), and 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (BAFPB) at a 2:2:1 molar ratio in N-methyl-2-pyrrolidone (NMP). A series of organosoluble, light-colored poly(amide-imide-imide)s (PAII, III_a-j) was prepared by triphenyl phosphite-activated polycondensation from the tetraimide-diacid I with various aromatic diamines (II_a-j). All the polymers were readily soluble in a variety of organic solvents such as NMP, N,N-dimethyl acetamide (DMAc), dimethyl sulfoxide, and even in less polar m-cresol and pyridine. Polymer films cast from DMAc had the cutoff wavelengths between 374 and 384 nm and had the b^∗ values in the range of 14.8-30.2. Polymers III_a-j afforded tough, transparent, and flexible films, which had tensile strengths ranging from 87 to 103 MPa, elongations at break from 11% to 37%, and initial moduli from 1.9 to 2.3 GPa. The glass transition temperatures of these polymers were in the range of 242-274 °C. They had 10% weight loss temperature above 526 °C and showed the char yield more than 55% residue at 800 °C in nitrogen.     

HET acid based oligoesters - TGA/FTIR studies

One of the important reactive halogenated dicarboxylic acids used in the synthesis of flame retardant unsaturated polyester resins is 1,4,5,6,7,7-hexachlorobicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (HET acid). In the present investigation four different oligoesters are synthesized using HET acid as the diacid component and 1,2-ethane diol, 1,2-propane diol, 1,3-propane diol and 1,4-butane diol as the aliphatic diols. Melt condensation technique in vacuum is used for the synthesis of the oligoesters. The number average molecular weights of the oligoesters are determined using end group analysis. The degree of polymerization is estimated to be 3-5. The structural characterization is done using FTIR and NMR (¹H and ¹³C) techniques. In the present investigation, TGA-FTIR studies for the different oligoesters are carried out in nitrogen atmosphere. The materials are heated from ambient to 600 °C at a heating rate of 20 °C/min. The main volatile products identified are CO, HCl, H₂O, CO₂, hexachlorocyclopentadiene and HET acid/anhydride. The evolution profile of these materials with respect to the structure of the oligoesters is discussed in detail and presented. The importance of β-hydrogens in the diol component and the plausible mechanism for the flame retardant behavior of these oligoesters are presented.     

Dephosphorylation of paraoxon by hydroxamate ions in micellar media

The rate-surfactant concentration profiles for the reaction of the insecticide paraoxon with hydroxamate ions (R(CO)·NHO⁻, R = CH₃, R = C₆H₅, R = 2-HOC₆H₄) in aqueous solutions of cetyltrimethylammonium salts, CTAX (X⁻ = Br⁻, Cl⁻, SO₃H⁻) have been measured at pH 11.0 at 30 °C. All these profiles are typical of micelle-assisted bimolecular reactions involving interfacial ion exchanges. The salicylhydroxymic acid-CTACl combination is most reactive.     

Thermal stability of solid and aqueous solutions of humic acid

The effects of temperature on the stability of a soil humic acid were studied in the present work. Solid samples of Gohy-573 humic acid (HA) and dissolved ones in aqueous solution (pH 6.0, 0.1 mol L⁻¹ NaClO₄) were investigated in order to understand the impact of temperature on the chemical properties of the material. The methods applied to solid samples in the present investigation were thermogravimetric analysis (TGA), temperature-programmed desorption coupled with mass spectrometry (TPD-MS), and in situ diffuse reflectance infrared Fourier transformed spectroscopy (in situ DRIFTS). Humic acid samples were studied in the 25-800 °C range, with focus on thermal/chemical processes up to 250 °C. The reversibility of the changes observed was investigated by cyclic changes to specified temperature ranges (40-110 °C). All measurements were conducted under inert-gas atmosphere in order to avoid samples combustion at increased temperatures. Aqueous solutions were analyzed by UV-vis absorption spectroscopy after storage at temperatures up to 95 °C, and storage times up to 1 week. For temperatures below 100 °C experiments on solid and aqueous samples have shown results which were consistent to each other. The amount of water desorbed is temperature dependent and up to 70 °C this process was totally reversible. Above 70 °C an irreversible loss of water was also observed, which according to UV-vis spectroscopy corresponds to water produced by condensation leading to more condensed polyaromatic structures. The water released up to 110 °C was about 7 wt% of the total mass of the dried humic acid, where less than 50% corresponded to reversibly adsorbed water. At higher temperatures (>110 °C), gradual decomposition resulting in the formation of carbon dioxide (110-240 °C), and carbon monoxide (140-240 °C) takes place. Hence, thermal treatment of Gohy-573 humic acid above 70 °C results in irreversible structural changes, that could affect chemical properties (e.g., complex formation) of the material.     

Preparation of 4(5)-vinylimidazole-co-acrylic acid copolymer and thermal performances related to applicability as PEM fuel cells

A series of acrylic acid and 4(5)-vinylimidazole copolymers for a non-hydrous proton transferring membrane used in polymer electrolyte membrane for fuel cell (PEMFC) are reported. The feed ratio of each monomer results in the variation of copolymer as evaluated by Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (¹H-NMR). Differential scanning calorimeter and thermal gravimetric analyzer confirm the thermal properties of copolymer films with T_g at 105-177 °C and T_d above 230 °C. The simultaneous analysis of wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) suggests the thermal performance about the decrease in domain size as a consequence of the loss of moisture content in the membrane and the increase in domain size as a consequence of chain mobility after T_g. The proton conductivities under anhydrous condition of the copolymer membranes are in the range of 10⁻² S/cm even up to 120 °C.     

Highly phosphonated polypentafluorostyrene: Characterization and blends with polybenzimidazole

In this study we present results of the conductivity and resistance to thermooxidative and condensation reactions of a highly phosphonated poly(pentafluorostyrene) (PWN2010) and of its blends with poly(benzimidazole)s (PBI). This polymer, which combines both: (i) a high degree of phosphonation (above 90%) and (ii) a relatively high acidity (pK_a (–PO₃H₂ ↔ –PO₃H⁻) ∼ 0.5) due to the fluorine neighbors, is designed for low humidity operating fuel cell. This was confirmed by the conductivity measurements for PWN2010 reaching σ = 5 × 10⁻⁴ S cm⁻¹ at 150 °C in dry N₂ and σ = 1 × 10⁻³ S cm⁻¹ at 150 °C (λ = 0.75). Furthermore, this polymer showed only 48% of anhydride formation when annealing it at T = 250 °C for 5 h and only 2% weight loss during a 96 h Fenton test. These properties combined with the ability of the PWN2010 to form homogeneous blends with polybenzimidazoles resulting in stable and flexible polymer films, makes PWN2010 a very promising candidate as a polymer electrolyte for intermediate- and high-temperature fuel cell applications.     

Direct hydroxylation of substituted benzenes to phenols with air and CO using molybdovanadophosphates as a key catalyst

A direct synthetic method of cresols from toluene by hydroxylation with air using CO as a reducing agent was developed. The reaction of toluene with air (15 atm) and CO (5 atm) in the presence of catalytic amounts of H₄PMo₁₁VO₄₀·31H₂O and Pd/C in aqueous acetic acid at 120 °C for 2 h afforded a mixture of o-, m-, and p-cresols in 9.9% yield at 83% selectivity. Cresols were obtained in 19% yield by recharging air and CO under these conditions. A variety of substituted benzenes were hydroxylated by this method to give the corresponding phenol derivatives in higher selectivity.