Green chemistry of polyurethanes: The catalytic <Emphasis Type="Italic">n</Emphasis>-butylaminolysis of ethylene carbonate as a model chain-growth reaction in the formation of nonisocyanate polyurethanes

The kinetic regularities and the mechanism of the catalytic action of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, which is the most active of the known catalysts for the formation of hydroxyurethanes from cyclocarbonates and amines, were studied using the example of the n-butylaminolysis of ethylene carbonate. In contrast with the noncatalytic reaction, which proceeds via two parallel pathways that involve one and two molecules of amine, the catalytic reaction follows a single pathway: the second molecule of amine is replaced by a molecule of the catalyst that accelerates the process in accordance with the mechanism of bifunctional catalysis. Different reaction pathways were studied by quantum chemical calculations based on the density functional method. It was shown that the high activity of 1,5,7-triazabicyclo[4.4.0]dec-5-ene results from the formation of a planar cation-like form of the catalyst. Moreover, the low-energy transition between the cation and the initial 1,5,7-triazabicyclo[4.4.0]dec-5-ene enables the catalyst to simultaneously be a good donor and acceptor of protons. This study presents a new way for finding among bifunctional organic compounds the catalysts that are even more active in the reaction of cyclocarbonates with amines.     

Spread of jet from an annular slit around an air intake

The results of an experimental investigation of the flow created by a conical jet spreading from a narrow slit around the periphery of a suction intake are described. The reorganization of the jet flow associated with the resulting three-dimensional flow structure is investigated. A flow scheme is proposed.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 2, pp. 187–190, March–April, 1991.     

Calculation of three-dimensional weakly expanding flow in jets and channels

The results are given of a calculation of laminar flow in a channel of square section and the motion of a turbulent jet from a cruciform nozzle in an ambient flow. To calculate the secondary flows, the field of the transverse velocity is decomposed into irrotational and solenoidal components. The results of the calculation of the flow in the channel are compared with the calculations of other authors and experimental data. To calculate the flow in the turbulent jet, a one-parameter turbulence model is used, and the influence of the inhomogeneity of the distribution of the longitudinal component of the velocity on the components of the Reynolds stress tensor is taken into account. The results of calculation of the flow in the jet behind a cruciform nozzle are compared with experimental data.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 4, pp. 36–44, July–August, 1984.     

Synthesis of isotactic polybutene-1 over titanium-magnesium catalysts with polydentate phosphine oxides as external electron donors

The polymerization of 1-butene over the TiCl₄/MgCl₂ (TMC) catalyst with the use of substituted phosphine oxides R _n P(O)(CH₂OR′)_{3 ? n} (R = alkyl, R′ = methyl or acyl, n = 0–2)—new external electron donors-has been investigated. The electron-donating (coordinating) centers in these compounds are the phosphoryl group (P=O) and the oxygen atoms of the substituents at the phosphorus atom. The dependence of the 1-butene polymerization activity of TMC on the nature of the substituents in the phosphine oxides has been studied. The microstructure, degree of crystallinity, molecular weight, and strain-strength characteristics of the synthesized polybutene-1 and the effect of hydrogen on these properties are reported. The most efficient external donor is Me₂P(O)CH₂OAc.     

Composite materials based on fullerenes C60/C70 and polypropylene prepared via in situ polymerization

New composite materials based on isotactic PP and fullerene were prepared via in situ polymerization with the use of an isospecific metallocene catalytic system. The stress-strain properties, thermophysical characteristics, and reactivities of composites in reactions of high-temperature decomposition, oxidation, and chemiluminescence were studied. The appreciable effect of fullerene on the thermal oxidation and crystallization behavior of composites (an increase in the crystallization temperature by 10 K) was found. It was shown that the protective inhibitory effect of fullerene in PP oxidation reactions is due to the interaction of fullerene nanoparticles with peroxy macroradicals.     

Ethylene polymerization and ethylene-1-hexene copolymerization over immobilized metallocene catalysts

Ethylene polymerization and ethylene-1-hexene copolymerization in the presence of metallocene catalysts based on Cp₂ZrCl₂, rac-Et(Ind)₂ZrCl₂, rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂, and rac-Me₂Si(2-Me-4-Ph-Ind)₂HfCl₂ been investigated. The catalysts have been immobilized on montmorillonite (MMT) containing methylaluminoxanes (MMT-H₂O)/AlMe₃ or isobutylaluminoxanes (MMT-H₂O)/ Ali-Bu₃ synthesized directly on the support surface. The immobilized catalysts, with the general formula (MMT-H₂O)/AlR₃/Zr(Hf)-cene, show a high activity comparable with the activity of the respective homogeneous systems, which depends on the nature of the metal and on the metallocene composition and structure. The catalytic properties of the metallocene systems depend strongly on the nature of the activator as a component of the catalytic complex. (MMT-H₂O)/Ali-Bu₃ is a more effective activator of the hafnocene precatalyst in the polymerization processes than oligomeric methylaluminoxane or methylaluminoxane synthesized on the support. The immobilization of the metallocenes on (MMT-H₂O)/AlR₃ leads to an increase in the molar mass of polyethylene and ethylene-1-hexene copolymers relative to the molar mass of the polymers synthesized using the respective homogeneous systems. The immobilized metallocene catalysts display high selectivity toward the insertion of a higher α-olefin (1-hexene) into the polymer chain, retaining this important property of their homogeneous counterparts.     

Effect of the chemical grafting of epoxy resin onto organomodified montmorillonite on the structure and heat resistance of an epoxy nanocomposite

It is shown that the noncatalyzed chemical grafting of an epoxy oligomer onto the surface of montmorillonite platelets may proceed via the reaction between the epoxy groups and the hydroxyl groups of the organic modifying agent of the layered aluminosilicate. The effect of grafting on the structure and heat resistance of the cured epoxy nanocomposite is studied. Complete exfoliation of montmorillonite particles into individual platelets is shown to be a necessary but insufficient condition for increasing the glass-transition temperature of the nanocomposite relative to that of the initial matrix. A much higher contribution to the increase in the glass-transition temperature is ensured by grafting of epoxy molecular chains onto the surface of aluminosilicate platelets; i.e., strong covalent matrix-aluminosilicate bonds form in addition to physical bonds, a process that entails development of a thicker three-dimensional network.     

Structure and dynamics of the ionospheric region with artificial small-scale irregularities according to complex measurements of the scattered radio-signal characteristics

We present the results of complex measurements of characteristics of HF radio signals scattered by artificial small-scale irregularities by means of oblique sounding using a chirp signal and by direction finding. On the basis of comparison of the experimental data and the calculations of aspect scattering of radio waves, the conclusion on the patch structure of an artificially disturbed ionosphere filled with small-scale field-aligned irregularities is drawn. The sizes of the patches amount to several ten kilometers, and they are separated by 100 or more kilometers. The drift speed of irregularities in the direction of the scattering vector in the plane perpendicular to the magnetic field is determined for several patches. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 51, No. 12, pp. 1011–1025, December 2008.