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.

A method is proposed for the regeneration of fire-resistant triaryl phosphate oils by heat treatment with anhydrous neutralizing agents with subsequent distillation of the reaction mixture. This treatment leads to the elimination of aging products in used triaryl phosphate oils such as acids, phenols, condensation products, wear metals, introduced sludge, and water. This method gives high yields of the regenerated oils meeting the standard requirements of fire-resistant triaryl phosphate oils for reuse.

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 method for the regeneration of used fire-resistant oils based on treating oils with an anhydrous neutralizing agent at heating, followed by rectification has been developed. As a result of such treatment, used triaryl phosphate oils are purified from a complex of aging products (acids, phenols, sealing products, wear metals, introduced sludge, water). The method provides high yieldsof regenerated oils with quality that meets the regulatory requirements for fire-resistant triaryl phosphate oils for reuse.

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.

The possibility of controlling the composition of a mixture of triphenyl phosphate, p-tert-butylphenyl diphenyl phosphate, di(p-tert-butylphenyl)phenyl phosphate, and tri(p-tert-butylphenyl) phosphate, formed by transesterification of triphenyl phosphate withp-tert-butylphenol, was demonstrated. The amount ofp-tert-butylphenol necessary for transesterification of triphenyl phosphate to yield a mixture of phosphates of required composition was determined. If necessary, the composition of the phosphates can be adjusted by selective distillation of triphenyl phosphate in a vacuum.

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%.

Based on systematized collection of Raman spectra of about 40 monounsaturated olefins, spectral patterns and invariant relations were established that formed the basis of the method for determining total olefins (total unsaturation per 100 carbon atoms) and their main classes in solutions of saturated hydrocarbons. Self-tuning of the model by calculating the proportion of spectrally unresolvable C=C components using the intensity of conjugated methyl groups increased its accuracy. In terms of repeatability, speed and cost-effectiveness of the analysis, the Raman-method is superior to standard methods of gas and adsorption chromatography and other modern spectralcorrelation methods. The accuracy and stability of the results repeatability is confirmed by more than annual series of parallel comparisons with the data of known method. It is shown that five types of olefins in paraffin model solutions are sufficient to construct calibration curves in units of the number of C=C bonds per 100 carbon atoms. These units make it possible to transform the data to the iodine scale and unify the calibration model for different fractions regardless of the hydrocarbon chain length. The Raman technique can be extended to analyze other mixtures of nonaromatic hydrocarbons and be used for remote control of processes via fi ber optic cables in industrial production.

Based on the systematized collection of the Raman spectra of about 40 monounsaturated olefins, spectral regularities and invariant relations were established that formed the basis of the method for determining total olefins (total unsaturation per 100 carbon atoms) and their main classes in solutions of saturated hydrocarbons. Self-adjusting of the model by calculating the proportion of spectrally unresolvable C=C components with the use of the intensity of conjugated methyl groups increased its accuracy. In terms of repeatability, speed and cost-effectiveness of the analysis, the Raman-method is superior to standard methods of gas and adsorption chromatography and other modern spectral-correlation methods. The accuracy and stability of the results repeatability is confirmed by more than annual series of parallel comparisons with the data of known method. It is shown that five types of olefins in paraffin model solutions are sufficient to construct calibration curves in units of the number of C=C-bonds per 100 carbon atoms. These units allow recalculating data to the iodine scale and unifying the calibration model for different fractions regardless of the length of the hydrocarbon chains. The Raman technique can be extended to analyze other mixtures of non-aromatic hydrocarbons and be used for remote control of processes via fiber optic cables in industrial production.

The possibility of using R n P(O)(CH 2 OR′) 3— n (R = alkyl, R′ = methyl or acyl, n = 0–2) polydentate phosphine oxides as external electron donors for the titanium-magnesium catalysts for isotactic polypropylene synthesis is demonstrated for the first time. The kinetics of propylene polymerization in liquid monomer at 70°C and the isotacticity and molecular-weight characteristics of the resulting polypropylene are studied as functions of the nature of the substituents at the phosphorus atoms in the external donor and the molar ratio of the cocatalyst AlEt 3 to the external electron donor. Among the compounds examined, isoamyldi(methoxymethyl)phosphine oxide (R = iso -Am, R′ = Me, n = 1) is the most efficient. The isotacticity index of the polypropylene (PP) synthesized on the titanium-magnesium catalyst with this external donor is as high as 94–95%, and the activity of the catalyst (Cat) in the absence of hydrogen is 5.0–6.5 (kg PP) (g Cat) −1 h −1 . With the optimum combination, the activity of this catalyst is ≈5 (kg PP) (g Cat) −1 h −1 and the isotacticity index is 94%. These parameters are close to those obtained for propylene polymerization in the absence of hydrogen on the same titanium-magnesium catalyst with phenyltriethoxysilane (external donor used in the industrial synthesis of PP): the activity is 5.6 (kg PP) (g Cat) −1 h −1 , and the isotacticity index is 95%. The introduction of hydrogen into the reaction zone makes it possible to efficiently control the molecular weight of PP, increases the catalyst activity by a factor of 1.5–2.5, and somewhat decreases the isotacticity index (from 94 to 91–92%).

The kinetics of propene hydroformylation in the presence of the catalytic system Rh(acac)(CO) 2 / n L (L = 2,2′-bis[(1,1′-diphenyl-2,2′-diyl)phosphito]-3,3′,5,5′-tetra- tert -butyl-1,1′-diphenyl, 0.5 < n < 20) in para -xylene at 90°C is reported. At n ≥ 2, the rate and regioselectivity of the process are independent of the L concentration. The reaction is of positive fractional order with respect to propene and hydrogen and of negative order with respect to CO. The molar ratio between the linear product and the branched product decreases with an increasing CO pressure and increases with an increasing H 2 pressure. The kinetic data are consistent with a process mechanism involving irreversible propene addition to the unsaturated hydride complex HRh(CO)L with the formation of the π-complex HRh(CO)L(C 3 H 6 ). The insertion of coordinated propene into the H-Rh bond of this complex is reversible in the linear aldehyde formation route and is quasi-equilibrium in the branched isomer formation route. The conclusions as to the character of these reaction steps are corroborated by the compositions of the but-1-ene and but-2-ene hydro-formylation products.

Isotactic poly(1-butene) (PB-1) shows a number of very interesting properties, a unique combination of excellent creep resistance and high flexibility being the most important. The polymer has the lowest flexural modulus of all plastics used for tube manufacturing. Owing to the valuable properties of PB-1, its production is increasing in spite of technological difficulties [1]. The industrial synthesis of poly( α -olefins) utilizes mainly TiCl 4 –MgCl 2 catalysts (TMCs) modified with electron-donor compounds capable of forming chelate complexes to increase isospecificity. At present, alkylalkoxysilanes are mainly used as such compounds (external donors, EDs) introduced with the AlEt 3 cocatalyst [1, 2]. At the same time, a search for other types of electron-donor components providing the necessary combination of catalyst properties is in progress. In this work, we studied for the first time the possibility of using polydentate phosphine oxides as electron-donor components of TMCs for the synthesis of isotactic poly( α -olefins). Here, we report the results of study of the polymerization of 1-butene on TMCs with external donors of the type R n P(O)(CH 2 OR') 3 – n (where R = alkyl; R' = methyl, acyl; n = 1, 2). Phosphine oxides— Me 2 P(O)CH 2 OMe (ED-I) [3], Me 2 P(O)CH 2 OC(O)Me (ED-II) [4], Bu 2 P(O)CH 2 OMe (ED-III) [5], and iso - AmP(O)(CH 2 OMe) 2 (ED-IV) [6]—were obtained by known procedures; commercial tributylphosphine oxide (ED-V) was also used. The polymerization of 1-butene was carried out on the TiCl 4 ‐MgCl 2 ‐dibutyl phthalate catalyst (Ti content was 2.06%) in a 200-mL metallic reactor equipped with a stirrer in n -heptane (110 mL) at 323 K and at a constant monomer concentration during polymerization. The solid component of the TMC was introduced after saturation of the solvent with 1-butene, and then solutions of the AlEt 3 cocatalyst and external donor in n -heptane were added. The polymerization time was 1 h. The catalyst activity was assessed from the ratio of the polymer yield to the amount of Ti, monomer concentration, and process duration. The degree of polymer isotacticity was determined from the content of the fraction insoluble in boiling diethyl ether [7]. The viscosity-average molecular weight M v was determined by viscometry in decalin at 383 K and calculated by the formula [8]

Data on changes in the activity of the Pd(dba)2/2TsOH/10Ph3P (dba is dibenzylideneacetone) and PdCl2(Ph3P)2/8Ph3P catalytic systems in the reaction of phenylacetylene with CO and n-butanol under the action of a solvent (aromatic hydrocarbons, chloroalkanes, ethers, esters, ketones, and dipolar aprotic media) are presented. The differences found in the response of either of the systems to changes in the properties of the medium are discussed in terms of a scheme of the catalytic cycle of reaction. It is noted that activity does not correlate with the physicochemical characteristics (polarity, basicity, and electron-acceptor ability) of solvents.

Condensation of the dichloride clathrochelate FeBd2(Cl2Gm)(BF)2 precursor (Bd2– is the α-benzyl dioxime dianion, Gm is the glyoxime residue) with quinoxaline-2,3-dithiol in the presence of triethylamine afforded the ribbed-functionalized quinoxaline clathrochelate. The structure of this complex was established by X-ray diffraction analysis.