Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation

The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10⁻⁶ to 3.1 × 10⁻⁵ mol Pt/mol CHCH₂. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10⁻⁶ mol of Pt per mol of CHCH₂, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH₂ groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007     

The effect of olefinic terminal chains on the mesomorphic properties of 4,4'-disubstituted diphenyldiacetylenes

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1-4; and X = C n H 2n + 1 , F, CF 3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF 3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices.

Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature.     

New Heat-Resistant Polyimidates Derived from Bisphenols and Mono- and Dicarboxylic Acid Imidoyl Chlorides

New polyimidates were prepared from bisphenols and mono- and dicarboxylic acid imidoyl chlorides. The structures of the polymers were determined, and their physicochemical, chemical, and thermal properties were studied. The possibility of preparing film and compression materials with good mechanical characteristics from these polymers was examined.     

Molecular Complexes of Crown Ethers in Crystals and Solutions

A review of the experimental and theoretical studies of the crown ether complexes with polar molecules in their crystals, solutions, and in a gas phase is given. The type of the molecular bonds in the complexes, their stoichiometry, and the change in the macrocycle conformation during complex formation are considered, as well as the effect of the macrocycle structure and the nature of the medium on the efficiency of the molecular bonding. New data are given on the enthalpies of transfer of the crown ethers from tetrachloromethane into solvents capable of forming hydrogen bonds. The enthalpies of specific interactions of macrocycles with the molecules of the solvents in the medium of the same solvents are characterized. The conformations of the crown ethers in the media under study are discussed.     

Formation of coherent spatial structures in the reaction-diffusion atmospheric system under the action of a planetary wave

On the example of the effect of an atmospheric wave with given amplitude on the density oscillations of minor gas constituents near the mesopause (at heights 80–90 km, we consider the influence of the quasi-resonant periodic spatial transport on a distributed system responding subharmonically to a periodic external action (diurnal sunlight variations). Numerical modeling revealed the formation of a coherent horizontal distribution of the dynamical variables (i.e., the concentrations of small constituents). Application of this effect to the mesopause conditions is discussed.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 47, No. 9, pp. 739–752, September, 2004.     

Finite element method in the solution of the Euler and Navier-Stokes equations for internal flow

Finite element solutions of the Euler and Navier-Stokes equations are presented, using a simple dissipation model. The discretization is based on the weak-Galerkin weighted residual method and equal interpolation functions for all the unknowns are permitted. The nonlinearity is iterated upon using a Newton method and at each iteration the linear algebraic system is solved by a direct solver with all unknowns fully coupled. Results are presented for two-dimensional transonic inviscid flows and two- and three-dimensional incompressible viscous flows. Convergence of the algorithm is shown to be quadratic, reaching machine accuracy in very few iterations. The inviscid results demonstrate the existence of nonunique numerical solutions to the steady Euler equations.     

Growth and study of single crystals of (Na,K)NbO<Subscript>3</Subscript> solid solutions

(Na, K)NbO₃ crystals with a perovskite structure and a KNbO₃ content up to 40 mol % were grown from flux with the use of the solvent NaBO₂. The dielectric measurements of the crystals grown revealed phase transitions that had never been observed before in ceramic samples.