Objectives. To study the equilibrium distribution of components between KU-2-8 sulfocationite and an aqueous solution containing picolinic acid and Cu(II); to show the possibility of immobilization of cations of picolinic acid and Cu²⁺ in sulfonic cation exchanger KU-2-8; to calculate the component compositions of the equilibrium solution, in order to obtain the required ionic composition of the KU-2-8 sulfonic cation exchanger according to the selectivity coefficients of binary ion exchange, and the constants of formation of such complexes in water.

Methods. The concentrations of the individual components in multicomponent solutions were calculated using the HySS 2009 program (Hyperquad Simulaton and Speciation). The calculation of the equilibrium ionic compositions of KU-2-8 sulfocationite was performed using the selectivity coefficients of binary ion exchanges and the formation constants of complexes of picolinic acid with Cu²⁺ and H⁺ cations. Experimental study of the equilibrium distribution of components between aqueous solutions of picolinic acid, copper nitrate, and KU-2-8 sulfocationite was carried out by means of the dynamic method at a temperature of 298 K. Fourier-transform infrared spectroscopy and electron paramagnetic resonance spectroscopy were used, in order to determine the ionic forms of the components contained in the sulfocationite.

Results. It was shown that the equilibrium solution contains H⁺ protons, Cu²⁺ cations, LH picolinic acid molecules, protonated picolinic acid cations [H₂L]⁺, deprotonated picolinic acid anions L-, Cu²⁺ complexes with the deprotonated picolinic acid anion [CuL]+, and Cu₂₊ complexes with two anions of deprotonated picolinic acid [CuL₂]. The concentration of H+, Cu²⁺, and [H₂L]⁺ cations in the solution significantly exceeds the concentration of other components at pH values from 0 to 0.5. The content of [CuL]⁺ cations and neutral complexes [CuL₂] increases significantly in the solution, while the [H₂L]⁺ cations disappear at pH greater than 1. It was experimentally established that the concentrations of picolinic acid and copper in the polymer phase are many times higher than the concentrations of these components in an aqueous solution. The partition coefficients are about 24 and 210 for picolinic acid and Cu(II), respectively. The calculated dependencies of the concentrations of Cu²⁺, [H2L]⁺, H⁺, [CuL]⁺ cations in the polymer vs pH of an equilibrium solution containing picolinic acid were obtained. The experimental data on the concentrations of all cations in the ion exchanger is in the intervals of the calculated compositions within the limits of measurement errors.

Conclusions. KU-2-8 sulfocationite is proposed as a container for obtaining drugs based on picolinic acid and Cu²⁺ cations. It was shown that the selectivity coefficients of binary ion exchanges and the formation constants of [H₂L]⁺, [CuL]⁺ complexes can be used to precalculate the ionic compositions of the equilibrium solution, in order to obtain the required compositions of the sulfocationite.

Objectives. To study the effect of a deep eutectic solvent (DES) based on glucose and citric acid on the vapor–liquid equilibrium of an aqueous solution of ethanol.

Methods. A qualitative and quantitative analysis of the conditions of vapor–liquid equilibrium in an ethanol–water–DES ternary mixture was performed based on the open evaporation method and the measurement of TPxy data using a Świętosławski ebulliometer. Since the volatility of the DES is negligible in comparison with that of water and ethanol, the composition of the vapor phase was measured by means of Karl Fischer titration. The conditions of vapor–liquid phase equilibrium were modeled using the UNIFAC model.

Results. The open evaporation method was used to determine the curves of residual concentrations for the ethanol–water–DES mixture at various DES concentrations and compositions (glucose–citric acid ratios). TPxy data was obtained for the mixture produced by adding 30 wt % DES to an aqueous solution of ethanol at atmospheric pressure. Studies show that DES based on glucose and citric acid has a significant effect on the relative volatility of ethanol in aqueous solution, leading to the disappearance of the azeotropic point. This effect is due to only the presence of glucose. Citric acid does not change the composition of the equilibrium phases, but rather increases the solubility of glucose in aqueous ethanol solutions. This is especially important at high ethanol concentrations, since glucose is poorly soluble in ethanol.

Conclusions. Addition of DES based on glucose and citric acid to an aqueous solution of ethanol leads to the disappearance of the azeotropic point. DES can thus be considered as a promising entrainer for extracting ethanol from aqueous solutions using extractive distillation. Modeling of the conditions of vapor–liquid equilibrium in the ethanol–water–DES system using the UNIFAC model showed a satisfactory level of accuracy. The error in the calculated data increases with increasing the glucose concentration, while remaining acceptable for practical use.

Objectives. Development of a domestic technology for producing environmentally friendly non-phthalate plasticizers, lubricants and transformer fluids based on neopentyl glycol (NPG), an oxo-synthesis product.

Methods. The methodology of the work was to study the kinetic laws of NPG esterification with acetic and 2-ethylhexanoic acids under self-catalysis conditions with an 8-fold molar excess of monocarboxylic acids. The production of NPG esters was carried out by azeotropic esterification in the presence of solvents—benzene and m-xylene. The resulting diesters were isolated from the reaction mass by vacuum rectification. The purity of the obtained NPG diesters was no less than 99.7 wt %. Analysis of the qualitative and quantitative composition of reaction samples was carried out using infrared spectroscopy, gas chromatography–mass spectrometry and gas–liquid chromatography.

Results. The paper presents the results of kinetic studies on NPG esterification of with acetic and 2-ethylhexanoic acids. It compares the reaction rates and reactivity of the acids used. Under the given conditions, NPG diesters were produced, and some of their physicochemical properties were determined. This enabled the data obtained to be used for the development of industrial technology in the production of NPG diesters.

Conclusions. It was established that with an eightfold molar excess of acid under self-catalysis conditions, a yield of NPG diacetate equal to 95% is achieved within 20–22 h at an optimal process temperature of 100–110℃; NPG di(2-ethylhexanoate)—within 26–28 h at 160–170℃. The activation energies and pre-exponential factors for the formation of NPG mono- and diesters with acetic and 2-ethylhexanoic acids were established. The paper presents the kinetic models of esterification.

Objectives. To synthesize 4,5-bis(diphenylphosphanyl)-H-1,2,3-triazole ligands and new chromium complexes based on them, in order to obtain a fraction of higher C₁₀–C₁₈ alpha-olefins from ethylene.

Methods. The Schlenk technique was used to obtain the target chromium complexes. Diphenylphosphanyl triazole ligands can be characterized by nuclear magnetic resonance spectroscopy. The composition of the final products was confirmed by elemental analysis. The liquid phase of the oligomerization reaction was studied by gas chromatography.

Results. L1–L9 ligands were obtained, and K1–K9 chromium complexes were synthesized based on the correspondent ligands using commercially available chromium (III) trichloride tris(tetrahydrofuran). The K1–K9 complexes thus obtained were tested in the process of ethylene oligomerization.

Conclusions. Chromium complexes based on 4,5-bis(diphenylphosphanyl)-H-1,2,3-triazoles K1–K9 were produced in high yields using the Schlenk technique. It was found that systems based on the K4–K7 and K9 complexes enable the ethylene oligomerization process to be carried out with a sufficiently high level of productivity. It was shown that the introduction of a dialkyl zinc derivative increases the performance and selectivity of the catalytic system for the target fraction.

Objectives. To create new polymer materials based on organosilicon derivatives of benzocyclobutene and to study the possibility of their use as insulating dielectric layers in micro- and microwave electronics devices.

Methods. The synthesis of the dibenzocyclobutyldimethylsilane (diBCB-DMS) monomer was carried out from 4-brombenzocyclobutene through the production stage of the Grignard reagent. Copolymers based on divinylbenzene and dibenzocyclobutyldimethylsilane were obtained by means of thermal polymerization. The properties and structure of the copolymers thus obtained were studied using the following methods: thermogravimetric analysis, infrared spectroscopy, nuclear magnetic resonance (NMR), mass spectroscopy, and by means of high-frequency measurements of volt-ampere characteristics and volumetric resonator.

Results. diBCB-DMS was synthesized with a yield of 81.5%. The composition and structure were confirmed by ¹H and ¹³C NMR spectroscopy. The dielectric constant of the diBCB-DMS homopolymer is ~2.6. The tangent of the dielectric loss angle at 1 GHz of the diBCB-DMS homopolymer is 2.3∙10⁻⁴. The tangent of the dielectric loss angle at 10 GHz of the diBCB-DMS homopolymer is 2.6∙10⁻⁴. The study of divinylbenzene and diBCB-DMS copolymers in different molar ratios on a thermogravimetric analyzer showed that the copolymers are able to withstand temperatures up to 470°C. The dielectric permittivity of diBCB-DMS and divinylbenzene copolymers in a molar ratio of 1 : 1 was 2.6. The values of the loss tangent at 1 and 10 GHz of copolymers in a molar ratio of 1 : 1 were 4.0∙10−4 and 5.6∙10⁻⁴, respectively.

Conclusion. Analysis of the obtained results shows that the samples of the diBCB-DMS homopolymer have the same dielectric characteristics as the samples based on diBCB-DMS and divinylbenzene, therefore, the introduction of divinylbenzene into the polymer structure does not worsen the dielectric parameters and such polimer materials can be used at high temperatures.

Objectives. To develop methods for the synthesis of substituted derivatives of the octahydrotriborate anion. Such compounds can be considered as hydrogen storage, components of ionic liquids, precursors for the production of boride coatings using the traditional chemical vapor deposition method, and also as a building material for the production of higher boron hydrogen clusters.

Methods. Since substitution reactions are sensitive to moisture and atmospheric oxygen, the syntheses were carried out in a direct flow of argon or in a dry, sealed SPEKS GB02M glove box with a double gas purification unit and two airlocks. The reaction was initiated by cooling to 0°C, in order to avoid the formation of by-products. All the results were characterized using infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies.

Results. The study presents a detailed study of the known methods for preparing substituted derivatives of the octahydrotriborate(1−) anion using dry hydrogen chloride as an electrophilic inductor and makes recommendations for improvement. In this method it is advisable to use cesium octahydrotriborate which facilitates the yield of the target product. New methods were proposed to initiate the substitution reaction in the [B₃H₈]⁻-anion using N-chlorosuccinimide and bromine. Using these inductors, new substituted derivatives of the octahydrotriborate anion with N-nucleophiles were obtained and defined by means of IR and NMR spectroscopies: [B3H7NCR], (R = Et, i-Pr, Ph) and [B₃H₇NH₂R], (R = C₉H₁₉ (INA), Bn), [B₃H₇NHEt₂], as well as Bu₄N[B₃H₇Hal], Bu₄N[B₃H₆Hal₂], where Hal = Cl, Br. It was also established that hydrogen bromide is released during the reaction with bromine and amines. This immediately protonates the amine which requires additional heating of the reaction mixture. The study also established that the reaction mechanism with N-chlorosuccinimide is not radical.

Conclusions. The main factors influencing the course of the substitution reaction are the possible occurrence of side interactions between the nucleophile and the inducer, steric possibilities, and subsequent isolation of the reactive reaction products.

Objectives. To examine the general principles and recent advances in the synthesis of high-purity and high-homogeneity barium titanate powders in the manufacture of electronic components.

Results. The main publications regarding the synthesis of barium titanate powder, including the works of recent years, were analyzed. The technological advantages and disadvantages of various synthesis methods were identified. Groups of methods based on solid-state interaction of reagents and methods of “wet chemistry” were also considered. The possibilities of producing barium titanate particles of non-isometric shapes for creating textured ceramics were discussed separately.

Conclusions. Barium titanate is a well-known ferroelectric with a high dielectric constant and low dielectric loss. It is used as a component in ceramic electronic products, for example, capacitors, memory devices, optoelectronic devices, and piezoelectric transducers. The possibilities of producing functional ceramics based on barium titanate powder largely depend on its state and morphological characteristics, determined during the synthesis stage. The most important factors affecting the functional characteristics of ceramics are the purity and morphology of the powder raw materials used.