R-Oxo hydroformylation processes on rhodium phosphite complexes developed at LLC «RN-RD CENTER» are described – selective production of n-butyral from propylene (R-Oxo I), production of a mixture of n-butyral and isobutyral in equal parts (R-Oxo II), selective production of n-pentanal from a mixture of linear butenes (R-Oxo III). A scheme for the hydroformylation of propylene with membrane separation of the catalyst from the heavy reaction products is described.The analysis of the direction of using C3–C5 oxosynthesis products as raw materials for the production of ester lubricants is carried out.

The data review of low molecular olefin C2-C4 hydroformylation as a key step of oxygenate compound oxosynthesis is presented. The industrial and perspective cobalt and rhodium organometallic catalytic systems modified with phosphine and phosphite ligands as well as the industrial technological schema of hydroformylation assisted with such a catalysts are demonstrated.

A review of scientific and patent data on the hydroformylation of lower C2–C4 olefins in the oxo synthesis of oxygen-containing products is presented. Industrial and prospective catalytic systems based on organometallic compounds of cobalt and rhodium modified with phosphine and phosphite ligands and also industrial technological schemes involving such catalytic systems are examined.

According to the data of 1 H NMR spectroscopy, trimethylolpropane, di(trimethylolpropane), linear formals, and structures including a fragment of a cyclic formal are the main components of the bottom residue after vacuum distillation of raw trimethylolpropane yielded in the technological process of n -butyral condensation with formaldehyde proceeding by the Cannizzaro–Tishchenko reaction. The content of other impurities is minor. The heavy bottoms can be converted in high yield to a mixture of esters of trimethylolpropane and di(trimethylolpropane) by esterification with n -pentanoic acid. Such esters are characterized by a low pour point, high chemical resistance, thermal stability, and good viscosity-temperature properties, as well as sufficient compatibility with various plastic materials, and therefore, can be employed as lubricants, polymer plasticizers, and other products.

The physicochemical properties and production of fire-resistant oils derived from triaryl phosphates are discussed. The method for obtaining butylated oil developed at the Rosneft United Research and Development Center is described. The application of this method for resuming the production of fire-resistant oils and hydraulic fluids using raw materials available in the Russian Federation is examined.

In this review, published information on the nature and molecular compositions of organochlorine compounds (OCCs), which are found in crude oil and in its refined products, is systematized. The native and added OCCs are reviewed. The formers are concentrated predominantly in high molecular weight resinous-asphaltene substances of crude oil, the latter’s, referred to as light organochlorine compounds, are present in the gasoline fractions. The following chemicals that are used for oil production are regarded as possible sources of OCCs: inhibited hydrochloric acid, acid compounds; organic solvents of asphalt-resin-paraffin deposits, organic solvents served for oil production stimulation, and possible products of a mutual solvent chlorination with hydrochloric acid.

Alcohols were obtained by the one-stage hydroformylation of olefins from the hydrocarbon fraction C 6 –C 9 , which was produced in the Fischer—Tropsch synthesis followed by the hydrogenation of aldehydes yielded by the hydroformylation products. The process is carried out on the cobalt catalyst modified by tertiary phosphines under the synthesis gas pressure 85 bar and temperature 180 °C. The role of the solvent is performed by paraffins of the hydrocarbon fraction from the Fischer—Tropsch synthesis. Cobalt acetylacetonate Co(acac) 2 , acetate Co(OAc) 2 , and carbonate CoCO 3 can serve as catalyst precursors. The complexes with bulky and basic phosphines were shown to possess satisfactory activity and high selectivity to alcohols. Tricyclohexyl- and triphenylphosphines are the most promising for the implementation of the process. The full conversion is achieved within 8 h at the cobalt concentration ∼0.2 wt.%: the residual olefin content is <1% and the selectivity to alcohols is ⩾97%.

Синтезированы четыре новых чередующихся узкозонных сополимера на основе бензодитиофена в условиях реакции Стилле. Все сополимеры обнаруживают хорошую растворимость в обычных органических растворителях и широкую абсорбцию в видимой области солнечного света по сравнению с гомополимерами бензодитиофена. Ширина запрещенной зоны полимерных пленок, полученная из вольтамперометрических данных, варьируется в пределах 1.34–2.28 эВ, а положение высшей занятой молекулярной орбитали в интервале 4.99–5.72 эВ. Напряжение холостого хода и эффективность полимерных солнечных фотоэлементов на основе синтезированных сополимеров лежат в интервале 0.22–0.65 В и 0.02–0.48% соответственно.

Four new low-band-gap alternating copolymers (P-1, P-2, P-3 and P-4) based on electron-rich benzodithiophene and newly developed electron-deficient units, thienopyrazine or dithiadiazatrindene derivatives, were synthesized by Stille polycondensation. All polymers exhibit good solubility in common organic solvents and a broad absorption band in the visible to near-infrared regions. The film optical band gaps of the polymers are in the range of 1.28–2.07 eV and the highest occupied molecular orbital (HOMO) energy levels are in the range of −4.99 eV to −5.28 eV. Bulk heterojunction polymer solar cells (PSCs) of the polymers were fabricated with phenyl-C61-butyric acid methyl ester (PC61BM) as acceptor material, and a power conversion efficiency of 0.80% was realized with P-1 as donor material.

New copolyfluorenes containing covalently bound iridium β-diketonate complexes (featuring high values of phosphorescence efficiency) in the backbone are synthesized through the targeted selection of molar ratios of monomers containing functional groups responsible for various irradiation regions under conditions of the Yamamoto reaction. All copolymers show solubility in organic solvents, such as DMF, DMAA, DMSO, toluene, THF, and chloroform, and feature reversible redox electrochemical properties. The electroluminescence spectra of the copolymers show broad intense bands in the visible region with maxima at 482–538 nm and a maximum brightness of 320 cd/m2 at a current density of 2900 A/m2. The iridium-containing copolyfluorenes are of interest as effective electroluminescent materials for light-emitting diodes.

New conjugated copolyfluorenes containing covalently bound quinolinolate complexes of iridium in the backbone are synthesized under conditions of the Yamamoto reaction. The structures and properties of the polymers are characterized via NMR spectroscopy, GPC, TMA, and TGA. All copolymers show solubility in common organic solvents and feature good thermal and thermo-oxidative properties. The absorption, luminescence, and electrochemical properties of the polymers are investigated. In thin films, the polymers emit blue light with wavelengths in the range 450–470 nm. The electroluminescence spectra of the copolymers show broad intense bands in the visible region with maxima at 500–525 nm corresponding to various emission colors with the chromaticity coordinates (0.361, 0.437) and (0.247, 0.411). The synthesized iridium-containing copolyfluorenes may be used as electron-hole transport materials in light-emitting diodes.

Two new alternating low band gap D-A copolymers with different acceptor structures of 4,8-bis-(5-bromothiophene-2-yl)-benzo[1,2,5]thiadiazole (P1) and 4,8-dithiophene-2-yl-benzo[1,2-c;4,5-c']-bis-[1,2,5]thiadiazole (P2) and a common BDT donor segment have been synthesized under Stille reaction conditions and characterized. The polymers showed good solubility, broad absorption bands and optical band gaps of 1.62 eV and 1.16 eV for P1 and P2, respectively. Bulk heterojunction (BHJ) polymer solar cells based on P1 and P2 as electron donors and fullerene derivatives (PC60BM and PC70BM) as acceptor were fabricated and their photovoltaic response was investigated. The overall power conversion efficieny (PCE) achieved for BHJ solar cells based on P1:PC60BM, P2:PC60BM, P1:PC70BM and P2:PC70BM blends cast from THF solvent is about 2.17%, 0.80%, 3.45% and 1.19%, respectively. The higher PCE for the device based on P1 has been attributed to the high value of hole mobility for P1 as compared to P2 and a larger driving force i.e. LUMO-LUMO offset, for photo-induced charge transfer for P1:PCBM BHJ active layer. The PCE has been further increased up to 5.30% and 1.58% for P1:PC70BM and P2:PC70BM blends cast from DIO/THF solvent, which is attributed to the improved crystallinity and a more balanced charge transport in the device.

Four new alternating narrow-band-gap copolymers based on benzodithiophene are synthesized under conditions of the Stille reaction. In comparison to benzodithiophene homopolymers, all these copolymers show good solubility in common organic solvents and broad absorption in the visible spectrum of sunlight. The band gaps of the polymer films, as estimated from the cyclic voltammetry data, vary within 1.34–2.28 eV, and the position of the highest occupied molecular orbital lies in the range 4.99–5.72 eV. The values of the open-circuit voltage and the efficiency of polymer solar cells based on the copolymers are within 0.22–0.65 V and 0.02–0.48%, respectively.

A number of new fluoroalkyl ether-containing polythiophenes are synthesized via oxidative polymerization in supercritical CO 2 (scCO 2 ) and chloroform. In both cases, high-molecular-mass polymers with high yields are prepared. The properties of the polymers synthesized in scCO 2 , such as molecular mass, polydispersity, conjugation, and UV absorption, are similar to the properties of the polymers obtained in chloroform. All poly(fluoroalkyl ether thiophenes) show solubility in DMF, toluene, THF, chloroform, and acetone. The glass-transition temperatures of the polymers are in the range 58–82°C, and the temperatures corresponding to 10% loss in their weight are in the ranges 248–294 and 260–303°C for poly(fluoroalkyl ether thiophenes) synthesized in scCO 2 and chloroform, respectively. All polymers fluoresce in the blue region with emission maxima at 506 to 526 nm. Because of the unique combination of fluoroalkyl and carbonyl groups, poly(fluoroalkyl ether thiophenes) feature good solubility in scCO 2 , which is a promising alternative solvent for the oxidative polymerization of fluoroalkyl ether thiophenes.

A new alternating copolymer P comprising of benzo[1,2-b;4,5,b']dithiophene (BDT) derivative and 4,9-bis-(5-bromothiophene-2-yl)-6,7-di-(2-ethylhexyl)[1,2,5]thiadiazolo[3,4-g]quinoxaline (DTQx) derivative electron, donating and electron withdrawing units, respectively, has been synthesized by Stille reaction. The copolymer was characterized by TGA, UV-visible absorption and cyclic voltammetry. The optical band gap of P was calculated from the onset wavelength of absorption to be about 1.38 eV. The copolymer P was used as electron donor along with PC60BM or PC70BM as electron acceptors for the fabrication of bulk heterojunction solar cells with configurations of ITO/PEDOT:PSS/P:PC60BM or PC70BM/Al. The power conversion efficiencies (PCE) of the copolymer solar cells blended with PC60BM and PC70BM as electron acceptors, spin cast from THF solvent, were 2.10% and 3.26%, respectively. The PCE device based on the P:PC70BM blend processed from DIO/THF was enhanced up to 4.47%. After optimizing the device parameters, such as blend ratio of P to PCBM and the choice of processing solvent, power conversion efficiency reaches as high as 5.12% for P:PC70BM blend, when processed from DIO/THF solvent, a blend ratio of 1 : 2 w/w and DMSO doped PEDOT:PSS buffer layer is used.

Four new alternating narrow band-gap copolymers containing benzodithiophene, 4,8-dithiophen-2-yl-benzo[1,2-c;4,5-c′-bis[1,2,5]thiadiazole, 4,9-bis(thiophen-2-yl)-6,7-di(2-ethylhexyl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline, 5,8-dibromo-2,3-bis(5-octylthiophen-2-yl)quinoxaline, and 4,7-bis(5-bromothiophen-2-yl)benzo[1,2,5] thiadiazole units are synthesized under Stille reaction conditions. The structures, molecular masses, and physical properties of the copolymers are studied via 1H NMR spectroscopy, GPC, cyclic voltammetry, and thermomechanical and thermogravimetric analyses. The polymers show solubility and a broad absorption region (with the band gap in the range from 0.81 to 1.53 eV). All of the polymers are photostable in air, and their levels of the highest occupied molecular orbital vary from −4.98 to −5.30 eV. Polymer solar cells based on these copolymers as donors and fullerene PC60BM as an acceptor show open-circuit voltages in the range 0.16–0.61 V, and the efficiencies of the devices are in the range 0.02–0.49%.

В условиях реакции Стиле синтезировано четыре новых чередующихся узкозонных сополимера, содержащих бензодитиофеновые, 4,8-дитиофен-2-ил-бензо[1,2-c;4,5-c]-бис-[1,2,5]тиадиазольные, 4,9-бис-(тиофен-2-ил)-6,7-ди(2-этилгексил)-[1,2,5]тиадиазоло[3,4-g]хиноксалиновые, 5,8-дибром-2,3-бис-(5-октилтиофен-2-ил)хиноксалиновые и 4,7-бис-(5-бромтиофен-2-ил)бензо[1,2,5]тиадиазольные структуры. Строение, молекулярная масса и физические свойства сополимеров исследованы с помощью спектроскопии ЯМР 1, ГПХ, циклической вольтамперометрии, термомеханического и термогравиметрического анализов. Полимеры обладают хорошей растворимостью, широкой абсорбцией (с шириной запрещенной зоны в пределах 0.81–1.53 эВ). Все полимеры фотостабильны на воздухе, уровень высшей занятой молекулярной орбитали находится в пределах от –4.98 до –5.30 эВ. Полимерные солнечные фотоэлементы на основе этих сополимеров в качестве доноров и фуллерена РС60 в роли акцептора показывают напряжение холостого хода в интервале 0.16–0.61 В и эффективность устройств в пределах 0.02–0.49%.