Influence of guests and protonation on the conformation of N,N′-dipyridyl-bis-aza-18-crown-6

Crystallisation of the sodium perchlorate adduct of N,N^′-dipyridyl-bis-aza-18-crown-6 from acidic aqueous conditions yielded [(H₃O)(N,N^′-dipyridyl-bis-aza-18-crown-6)][ClO₄] and [Na·N,N^′-dipyridyl-bis-aza-18-crown-6]₂ [(H⁺)₂N,N^′-dipyridyl-bis-aza-18-crown-6][ClO₄]₄·2H₂O. The conformations of crown ethers were significantly influenced by incorporation of an H₃O⁺ or sodium ion, or protonation of the amino nitrogen atoms resulting in three different structures for the macrocycle.     

Physical and chemical effects of diethyl N,N′-diethanolaminomethylphosphate on flame retardancy of rigid polyurethane foam

Diethyl N,N-diethanolaminomethylphosphate could react with isocyanate because it contained hydroxy group. This was confirmed by FTIR spectrum. It did not produce any effect on the foam structure of rigid polyurethane foam (RPUF). SEM, IR spectrum, and thermal analysis were used for investigation of the physical and chemical changes during the combustion of flame-retardant RPUF. It was shown that the flame retardancy changed the thermal decomposition behavior of RPUF, widened the decomposition temperature region of RPUF, reduced the amounts of decomposition products at high temperatures, and increased the decomposition residuals arisen from charring of flame-retardant RPUF. Those changes improved the flame retardancy of RPUF. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 276–282, 2001     

Dependence of Specific Impulse of Metal-free Formulations on CHNO-oxidizer′s Element Content and Enthalpy of Formation

It is shown that it is not correct to estimate energetic characteristics of different compounds of solid composite propellants by evaluation of the specific impulse values of these components serving as an only component in the formulation.Such an approach may turn the researcher to a wrong conclusion.One has to compare compound′s potential in formulations close to real,e.g.at least with necessary amount of binders.Dependences of specific impulse upon element content of highenthalpy CHNO oxidizer,its enthalpy of formation,and kind of binder have been found.     

Synthesis of N,N′-Dimethyl-N,N′-Dioctyl-3-Oxadiglycolamide and its Extraction Properties for Lanthanides

Abstract

Tetraalkyl-3-oxadiglycolamides show good prospects in nuclear reprocessing because of their complete incinerability. In addition, their degradation products interfere much less in the separation process when compared with organophosphorus extractants. An asymmetric extractant, N,N′-dimethyl-N,N′-dioctyl-3-oxadiglycolamide, has been synthesized by a five-step process. The compound was applied to the extraction of selected lanthanides from nitric acid solutions using chloroform as diluent. Its extraction properties for lanthanides from nitrate media have been described. The distribution ratio of the selected metal ions has been studied as a function of aqueous HNO₃ concentrations, diglycolamide concentration and temperature.     

Synthesis and Evaluation of N,N′-dimethyl-N,N′-dicyclohexyl-Malonamide (DMDCMA) as an Extractant for Actinides

A malonamide based extractant, i.e., N,N′-dimethyl-N,N′-dicyclohexyl-malonamide (DMDCMA) was synthesized in a single step and tested for the extraction of several actinide ions such as Am(III), U(VI), Np(IV), Np(VI), Pu(IV), Pu(VI), etc., from nitric acid medium. The extractant was soluble in phenyltrifluoromethylsulphone (PTMS or FS-13) unless stated otherwise. The effect of various experimental parameters, such as the aqueous phase acidity (0.01–3 M HNO₃), nature of the acid, oxidation states of the metal ions, ligand concentration, nature of the diluent and temperature on the extraction behavior of metal ions was studied. The extracted Am(III) species was determined from slope analysis method as [Am(NO₃)₃(DMDCMA)₂]. The extraction of the metal ions was found to increase with the aqueous phase acidity. The temperature variation studies allowed the calculation of the heat of the two-phase extraction reaction as well as the corresponding extraction constants. These studies revealed that DMDCMA showed good extraction for all the actinide metal ions investigated, and have the advantage of single stage synthesis and easier purification protocol.     

Extraction of Lanthanides with N,N′‐Dimethyl‐N,N′‐diphenyl‐malonamide and ‐3,6‐dioxaoctanediamide

Abstract

The extraction properties of the trivalent lanthanides (Ln(III)) with the bidentate N,N′‐dimethyl‐N,N′‐diphenyl‐malonamide (MA) and the tetradentate N,N′‐dimethyl‐N,N′‐diphenyl‐3,6‐dioxaoctanediamide (DOODA) were investigated. These diamides formed by coupling two amide groups with methylene and/or ether groups are bidentate for the MA and tetradentate for the DOODA. By adding a previous data regarding the tridentate N,N′‐dimethyl‐N,N′‐diphenyl‐diglycolamide (DGA), these extraction results enabled us systematically study an effect of number of oxygen donor on its extraction behavior of Ln(III). The change in the distribution ratios (Ds) of Lu(III) with an increase in the HNO₃ concentration is greater than that of La(III) in both the MA and DOODA systems. Therefore, the relationship between the D and atomic number, i.e., the lanthanide pattern, changes with the HNO₃ concentration: the Ds decrease with an increasing atomic number at lower HNO₃ concentrations. The Ds of the lighter Ln(III) are similar to the Ds of the heavier Ln(III) at higher HNO₃ concentrations. The number of the extractant in the extracted species for La(III) and Lu(III) obtained from slope analysis at 4 M HNO₃ in the MA system are about 3, while those in the DOODA system are quite different, i.e., 2 for La(III) and 1.5–3 for Lu(III). The comparison of the extractability of Ln(III) by MA, DOODA, and DGA shows that the magnitude of the Ds is in the sequence of MA < DOODA ? DGA. This suggests the introduction of one ether oxygen atom to the principal chain in the diamides leads to a good extractability for the Ln(III) from HNO₃ solution.     

Improvement of water resistance of wheat flour-based adhesives by thermal–chemical treatment and chemical crosslinking

A water-resistant adhesive for plywood panels for engineered wood floors was developed using thermal–chemically treated wheat flour (WF), polyvinyl alcohol (PVA), and polymeric diphenylmethane diisocyanate (p-MDI) as the cross-linker. The thermal–chemical treatment was performed at 100°C in the presence of sulfuric acid or sodium dodecyl sulfate (SDS). Fourier transform infrared spectroscopy, X-ray diffraction spectroscopy, and scanning electron microscopy were used to investigate the chemical structure, crystalline degree, and morphology change, respectively, of the thermal–chemically treated WF. The boiling water-insoluble content and acetaldehyde values of the thermal–chemically treated WF were also evaluated and compared with those of the controls—native WF and thermally treated WF alone. The bond property evaluation showed that the water resistance of the thermal-SDS-treated WF (T-SDS-WF)-based adhesive was significantly improved, which is mainly attributed to the formation of a three-dimensional crosslinking network resulting from self-crosslinking of the wheat protein, the Maillard reaction between the wheat starch and wheat protein, and the increased crosslinking between T-SDS-WF and p-MDI. Overall, the developed WF-based adhesive is a promising bio-based candidate in the production of plywood for engineered wood floors.     

Effect of Anions on the Extraction of Lanthanides (III) by N,N′‐Dimethyl‐N,N′‐Diphenyl‐3‐Oxapentanediamide

Abstract

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y by N,N′‐dimethyl‐N,N′‐diphenyl‐3‐oxapentanediamide (DMDPhOPDA) in 1,2‐dichloroethane from aqueous media containing ClO₄ ^?, PF₆ ^?, (CF₃SO₂)₂N^? anions or by DMDPhOPDA in 1,2‐dichloroethane in the presence of 1‐butyl‐3‐methylimidazolium bis[(trifluoremethyl)sulfonyl]imide ([C₄mim][Tf₂N]) and 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([C₄mim][PF₆]) from HNO₃ solutions has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. The addition of HPF₆ and (CF₃SO₂)₂NH or their salts to the aqueous HNO₃ or HCl solutions leads to an enchancement of lanthanides (III) extraction by DMDPhOPDA. A considerable synergistic effect was observed in the presence of ionic liquids (IL) in the organic phase containing DMDPhOPDA. This effect is connected with the hydrophobic nature of the IL anion. The distribution of ILs between the equilibrium organic and aqueous phases can govern the extractability of lanthanides (III) in DMDPhOPDA‐IL systems.     

Rhodium catalyzed hydroformylation of 1-decene in low melting mixtures based on various cyclodextrins and N,N′-dimethylurea

Different low melting mixtures (LMMs) based on N,N′-dimethylurea (DMU) and various cyclodextrin (CD) derivatives were synthetized. The melting point was weakly affected by the size and the chemical modification of CD. By contrast, the chemical modification of CD led to a decrease in viscosity of the LMMs. These mixtures were evaluated as solvent in rhodium-catalyzed hydroformylation reaction of 1-decene. The LMM based on DMU/RAME-β-CD (70/30) allowed reaching the highest catalytic activity (1980 h^− 1). The influence of several factors was studied and it was established that the conversion increased with the 1-decene solubility and decreased with the LMM viscosity.     

Effect of the fractional composition of the solid components of coal–water fuel on the characteristics of ignition and combustion

The experimental results of studies of the ignition and subsequent combustion processes of the single drops of organic coal–water fuels (OCWFs) arranged on the junction of a quick-response thermocouple (thermal inertia, <1 s) in an atmosphere of heated (600–1000 K) air are presented. The particles of 2B brown coal and D coal, water, and oils of different types (turbine, motor, and transformer oils) were used as the main OCWF components. The effect of the degree of grinding (fineness) of the solid fuel components of OCWFs on the following integral characteristics of the ignition and combustion of prepared fuel compositions was established: the delay times of ignition and complete combustion. A decrease in the delay times of ignition and complete combustion with decreasing the degree of grinding was detected (in a range of 40–200 μm used as an example). The reasons and special features of the influence of this factor on the integral characteristics of the test processes were recognized.     

Influence of the temperature dependence of the thermophysical properties of coal–water fuel on the conditions and characteristics of ignition

The results of an experimental study and mathematical simulation of the ignition of coal–water fuel (CWF) particles, the main thermophysical characteristics of which (thermal conductivity (λ), heat capacity (C), and density (ρ)) depend on temperature, are reported. Based on the results of the numerical study, the influence of changes in the thermophysical properties upon the heating of the main bed of fuel on the conditions and characteristics of its ignition was analyzed. The ignition delay times (t _i) of CWF particles were determined under the typical furnace conditions of boiler aggregates. As a result of the mathematical simulation of the process of CWF ignition, it was established that the temperature dependence of thermophysical characteristics can exert a considerable effect on the characteristics and conditions of ignition. In this case, it was found that the ignition of coal–water drops is possible under the conditions of their incomplete dehydration. A good agreement of the theoretical ignition delay times of the CWF particles and the experimental values of t _i was established.     

Interaction and dispersion stability of alumina suspension with PAA in N,N′-dimethylformamide

The alumina suspension in N,N′-dimethylformamide (DMF) was studied in the presence of a polyacrylic acid (PAA) dispersant. The sedimentation measurements of the suspensions show that PAA can impart favorable dispersion stability to alumina in DMF over a wide apparent pH (pH_a) range. The adsorption of PAA on alumina and the zeta potential of the suspension are pH_a dependent. FTIR-ATR spectroscopic studies reveal that the different interaction mechanisms between PAA and alumina work as a function of pH_a. But the observable difference of dispersion between pH_a values of 2.6–12.7 is small according to the sedimentation experiments. This can be explained by a combination of the static effect of PAA dispersant and different sizes of steric barrier resulting from the configurational variation of PAA with changing pH_a values.     

Synthesis and properties of polysiloxane containing N,N′-bis(diphenylsilyl)tetraphenylcyclodisilazane

A new kind of polysiloxane containing N,N′-bis(diphenylsilyl)tetraphenylcyclodisilazane was prepared by the anionic polymerization with a “seed solution” as initiator. The synthesis of monomers N,N′-bis(hydroxydiphenylsilyl)tetraphenylcyclodisilazane (BHPTPC), N,N′-bis(chlorodiphenylsilyl)tetraphenylcyclodisilazane (BCPTPC), and 1,3-dichloro-1,1,3,3-tetraphenyldisilazane (DCTPS) are all reported in this study. The synthesized polysiloxane containing N,N′-bis(diphenylsilyl)tetraphenylcyclodisilazane was characterized by ¹H–NMR, ²⁹Si–NMR, gel permeation chromatography (GPC), and intrinsic viscosity. The thermal stability of the polysiloxane was studied by isothermal gravimetric analysis (IGA). The results demonstrated that the synthesized polysiloxane containing N,N′-bis(diphenylsilyl)tetraphenylcyclodisilazane had excellent thermal stability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 929–933, 2001     

Pseudokinetics for the copolymerization of butadiene and styrene produced using n-butyl lithium and N,N,N′,N′-tetramethylethylenediamine,considering different reactivities of the structural units

The anionic solution copolymerization of butadiene and styrene prepared by anionic living polymerization using an initiator composed of n-butyl lithium, and N,N,N′,N′-tetramethylethylenediamine as active center modifier was modeled as a tetrapolymerization. The kinetic model proposed considering that the reactivity of the active sites is different because of varying configurations cis, trans, vinyl, and styryl. From the reaction scheme expressions to rate of monomers consumption, microstructure and dyad formation were obtained. With the first-order Markov model, the expressions for the fraction of active sites and dyad distribution as a function of the conditional probabilities were obtained. Therefore, the model proposed is different to kinetic models previously reported, because it allows obtaining the parameters kinetic in order to know the distribution of the isomeric species presents in the copolymerization of butadiene and styrene, and the intrinsic reactivity of configurational active sites. The rate constants were determined by fitting to the conversion and dyad experimental data using the nonlinear least square method. The experimental data reported in the literature, monomer conversion and microstructure, in addition to dyad sequence distribution were correctly predicted.     

Research on curing mechanism and thermal property of bis-allyl benzoxazine and N,N′-(2,2,4-trimethylhexane-1,6-diyl) dimaleimide blend

A blend of 2,2′-bis(8-allyl-3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) propane (Bz-allyl) and N,N′-(2,2,4-trimethylhexane-1,6-diyl) dimaleimide (TBMI) was prepared. The curing mechanism and thermal property of the cured blend were studied with Differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) and Dynamic mechanical analysis (DMA). It was found that in BzT11 the thermal polymerization reaction of TBMI, the reaction of TBMI catalyzed by Bz-allyl, Ene reaction between TBMI and allyl groups occurred at a low temperature (160 °C) simultaneously. About 20% of TBMI was consumed by Ene reaction. Besides, seldom oxzine ring of Bz-allyl polymerized at a low temperature (160 °C) and most oxzine ring of Bz-allyl reacted at a high temperature (over 160 °C). The T_g of cured blends was increased with the increment of the proportion of TBMI in the blends.