Особенности синтеза сложных эфиров пентаэритрита и алифатических карбоновых кислот изомерного строения

Objectives. Due to their structures, pentaerythritol esters have a number of appealing properties such as high viscosity index when used as oils and excellent compatibility with polyvinyl chloride when used as plasticizers. For the production of pentaerythritol and carboxylic acids, natural gas can be used as a feedstock, which implies a strategic development of the petrochemical industry, a decrease in the amount of gas used for combustion, and its applications for the production of chemical products.Methods. The synthesis process was conducted in a self-catalysis mode with excess acids in a molar ratio of 8:1 and in the presence of a solvent (toluene) of ~30% per reaction mass. This ensures a uniform distillation of the reaction water at a constant temperature of 100–110 °C, a decrease in the side reaction products, and an increase in process selectivity. The products from the reaction mass were isolated by vacuum distillation, and identification of all the synthesized tetraesters was performed by chromatography–mass spectrometry analysis.Results. This work proposes options for optimizing the conditions of the thermal esterification of pentaerythritol with isomeric monocarboxylic acids (isobutyric, isovaleric, pivalic, and 2-ethylhexanoic acids) that have different reactivities due to their structures. Methods for isolating tetraesters of pentaerythritol and corresponding acids have been developed. The characteristics of the main series of ions of tetraesters of pentaerythritol and aliphatic isomeric acids C4–C8 in the mass spectra were obtained.Conclusions. The yields of tetraesters were at 95%–96% of the theoretical value, and product purity was >99.6%. The resulting target products (tetraesters) were characterized by relative color stability, where the maximum degree of color after cleaning was less than 20 units according to Hazen (180 units for tetra-2-ethylhexnoate), which corresponds to the standards in GOST 29131-91 (ISO 2211-73). The esterification rates were compared, and it was shown that the quantitative yields of isomeric tetraesters at 100–110 °C were achieved in 12–15 h for isobutyric and isovaleric acids, 25–27 h for 2-ethyl-hexanoic acid, and ~40 h for pivalic acid.  Цели. Сложные эфиры пентаэритрита за счет своей структуры обладают рядом привлекательных свойств: высоким индексом вязкости при их использовании в качестве масел и отличной совместимостью с поливинилхлоридными (ПВХ) полимерами при их использовании в качестве пластификаторов. При этом исходным сырьем для производства как пентаэритрита, так и карбоновых кислот может служить природный газ, что актуально с точки зрения снижения объемов газа, направляемого на сжигание, и его использование в производстве химической продукции. Цель работы – разработка новых методов синтеза тетраэфиров пентаэритрита и алифатических изомерных кислот С4–С8.Методы. Процесс проводили в режиме самокатализа при избытке кислоты в мольном соотношении 8:1, а также в присутствии растворителя (толуола) ~30% на реакционную массу, обеспечивающего равномерный отгон реакционной воды при постоянной температуре 100–110 °С, уменьшение продуктов побочных реакций и повышение селективности процесса. Продукты из реакционной массы выделяли методом вакуумной ректификации. Идентификация всех синтезированных тетраэфиров проведилась с использованием хроматомасс-спектрометрического анализа.Результаты. В работе предложены варианты оптимизации условий термической этерификации пентаэритрита изомерными монокарбоновыми кислотами (изомасляной, изовалериановой, пивалевой, 2-этилгексановой), обладающими за счет своей структуры различной реакционной способностью. Разработаны методики выделения тетраэфиров пентаэритрита и соответствующих кислот. Получены характеристики основных серий ионов тетраэфиров пентаэритрита и алифатических изомерных кислот С4–С8 в масс-спектрах.Выводы. В предложенных условиях проведения процесса выход тетраэфиров составил 95–96% от теоретического с чистотой не менее 99.6%. Полученные целевые продукты (тетраэфиры) характеризуются относительной цветостабильностью: максимальная степень окрашенности после очистки составляет не более 20 ед. по Хазену (для тетра-2-этилгексаноата – 180), что соответствует ГОСТ 29131-91 (ИСО 2211-73). Количественные выходы изомерных тетраэфиров при 100–110 °С достигаются: за 12–15 ч для изомасляной и изовалериановой кислоты, 25–27 ч для 2-этил-гексановой и ~40 ч для пивалевой кислоты

Challenges and research priorities to understand interactions between climate, ice sheets and global mean sea level during past interglacials

Quaternary interglacials provide key observations of the Earth system's responses to orbital and greenhouse gas forcing. They also inform on the capabilities of Earth system models, used for projecting the polar ice-sheet and sea-level responses to a regional warmth comparable to that expected by 2100 C.E. However, a number of uncertainties remain regarding the processes and feedbacks linking climate, ice-sheet and sea-level changes during past warm intervals. Here, we delineate the major research questions that need to be resolved and future research directions that should be taken by the paleoclimate, sea-level and ice-sheet research communities in order to increase confidence in the use of past interglacial climate, ice-sheet and sea-level reconstructions to constrain future predictions. These questions were formulated during a joint workshop held by the PAGES-INQUA PALSEA (PALeo constraints on SEA level rise) and the PAGES-PMIP QUIGS (QUaternary InterGlacialS) Working Groups in September 2018.PAGE

Thermal Structure and Aerosols in Mars’ Atmosphere From TIRVIM/ACS Onboard the ExoMars Trace Gas Orbiter : Validation of the Retrieval Algorithm

Funding Information: ExoMars is a space mission of ESA and Roscosmos. The ACS experiment is led by IKI, the Space Research Institute in Moscow, Russia, assisted by LATMOS in France. This work, exploiting ACS/TIRVIM data, acknowledges funding by CNES. The science operations of ACS are funded by Roscosmos and ESA. R. M. B. Young acknowledges support from UAE University grants G00003322 and G00003590. ACS/TIRVIM team at IKI acknowledges the subsidy of the Ministry of Science and High Education of Russia. The authors warmly thank Michael Smith and another anonymous reviewer for their thorough review of our manuscript. Publisher Copyright: © 2022 The Authors.Peer reviewe

The Atmospheric Chemistry Suite (ACS) of Three Spectrometers for the ExoMars 2016 Trace Gas Orbiter

The Atmospheric Chemistry Suite (ACS) package is an element of the Russian contribution to the ESA-Roscosmos ExoMars 2016 Trace Gas Orbiter (TGO) mission. ACS consists of three separate infrared spectrometers, sharing common mechanical, electrical, and thermal interfaces. This ensemble of spectrometers has been designed and developed in response to the Trace Gas Orbiter mission objectives that specifically address the requirement of high sensitivity instruments to enable the unambiguous detection of trace gases of potential geophysical or biological interest. For this reason, ACS embarks a set of instruments achieving simultaneously very high accuracy (ppt level), very high resolving power (>10,000) and large spectral coverage (0.7 to 17 μm—the visible to thermal infrared range). The near-infrared (NIR) channel is a versatile spectrometer covering the 0.7–1.6 μm spectral range with a resolving power of ∼20,000. NIR employs the combination of an echelle grating with an AOTF (Acousto-Optical Tunable Filter) as diffraction order selector. This channel will be mainly operated in solar occultation and nadir, and can also perform limb observations. The scientific goals of NIR are the measurements of water vapor, aerosols, and dayside or night side airglows. The mid-infrared (MIR) channel is a cross-dispersion echelle instrument dedicated to solar occultation measurements in the 2.2–4.4 μm range. MIR achieves a resolving power of >50,000. It has been designed to accomplish the most sensitive measurements ever of the trace gases present in the Martian atmosphere. The thermal-infrared channel (TIRVIM) is a 2-inch double pendulum Fourier-transform spectrometer encompassing the spectral range of 1.7–17 μm with apodized resolution varying from 0.2 to 1.3 cm−1. TIRVIM is primarily dedicated to profiling temperature from the surface up to ∼60 km and to monitor aerosol abundance in nadir. TIRVIM also has a limb and solar occultation capability. The technical concept of the instrument, its accommodation on the spacecraft, the optical designs as well as some of the calibrations, and the expected performances for its three channels are described

North Pacific twentieth century decadal-scale variability is unique for the past 342 years

Reconstructed sea surface temperatures (SSTs) derived from Mg/Ca measurements in nine encrusting coralline algal skeletons from the Aleutian archipelago in the northernmost Pacific Ocean reveal an overall increase in SST from 1665 to 2007. In the Aleutian SST reconstruction, decadal-scale variability is a transient feature present during the 1700s and early 1800s and then fully emerging post-1950. SSTs vary coherently with available instrument records of cyclone variance and vacillate in and out of coherence with multicentennial Pacific Northwest drought reconstructions as a response to SST-driven alterations of storm tracks reaching North America. These results indicate that an influence of decadal-scale variability on the North Pacific storm tracks only became apparent during the midtwentieth century. Furthermore, what has been assumed as natural variability in the North Pacific, based on twentieth century instrumental data, is not consistent with the long-term natural variability evident in reconstructed SSTs predating the anthropogenic influence

Цимолы. 1. Современное состояние процессов получения цимолов

The article analyzes methods for the preparation of cymenes based on using petrochemical raw materials: toluene and propylene/isopropanol. It is concluded that at present advanced technologies for the production of individual cymenes are absent, and the heterogeneous catalytic processes require significant improvement.Проанализированы методы получения цимолов, базирующиеся на использовании нефтехими-ческого сырья - толуола, пропилена/изопропилового спирта. Сделан вывод о том, что в настоящее время отсутствуют совершенные технологии получения индивидуальных цимолов, а гетерогенно-каталитические процессы требуют серьезной доработки

Цимолы. 2. Алкилирование толуола на сульфокатионите Amberlyst 36 dry

The possibilities of obtaining cymene by toluene alkylation with propylene on sulfocationite Amberlyst 36 Dry were estimated experimentally . The main characteristics of the process are given, and their analysis is presented.Экспериментально оценены возможности процесса получения цимолов алкилированием толуола пропиленом на сульфокатионите Amberlyst 36 Dry . Приведены основные характеристики процесса , дан их анализ

Best-of-Three Contests: Experimental Evidence

We conduct an experimental analysis of a best-of-three Tullock contest. Intermediate prizes lead to higher efforts, while increasing the role of luck (as opposed to effort) leads to lower efforts. Both intermediate prizes and luck reduce the probability of contest ending in two rounds. The patterns of players‟ efforts and the probability that a contest ends in two rounds is consistent with „strategic momentum‟, i.e. momentum generated due to strategic incentives inherent in the contest. We do not find evidence for „psychological momentum‟, i.e. momentum which emerges when winning affects players‟ confidence. Similar to previous studies of contests, we find significantly higher efforts than predicted and strong heterogeneity in effort between subjects

Seasonal changes in the vertical structure of ozone in the Martian lower atmosphere and its relationship to water vapour

The mid-infrared channel of the Atmospheric Chemistry Suite (ACS MIR) onboard the ExoMars Trace Gas Orbiter is capable of observing the infrared absorption of ozone (O3) in the atmosphere of Mars. During solar occulations, the 003←000 band (3000-3060 cm-1) is observed with spectral sampling of ∼0.045 cm-1. Around the equinoxes in both hemispheres and over the southern winters, we regularly observe around 200-500 ppbv of O3 below 30 km. The warm southern summers, near perihelion, produce enough atmospheric moisture that O3 is not detectable at all, and observations are rare even at high northern latitudes. During the northern summers, water vapour is restricted to below 10 km, and an O3 layer (100-300 ppbv) is visible between 20-30 km. At this same time, the aphelion cloud belt forms, condensing water vapour and allowing O3 to build up between 30-40 km. A comparison to vertical profiles of water vapour and temperature in each season reveals that water vapour abundance is controlled by atmospheric temperature, and H2O and O3 are anti-correlated as expected. When the atmosphere cools, over time or over altitude, water vapour condenses (observed as a reduction in its mixing ratio) and the production of odd hydrogen species is reduced, which allows O3 to build up. Conversely, warmer temperatures lead to water vapour enhancements and ozone loss. The LMD Mars Global Climate Model is able to reproduce vertical structure and seasonal changes of temperature, H2O, and O3 that we observe. However, the observed O3 abundance is larger by factors between 2 and 6, indicating important differences in the rate of odd-hydrogen photochemistry