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.     

Integrable models for vicious and friendly walkers

We consider random walks of two essentially different classes of random walkers, namely, of vicious and friendly ones, on one-dimensional lattices with periodic boundary conditions. The walkers are called vicious since, arriving at a lattice site, they annihilate not only one another but all the remaining walkers as well. On the contrary, an arbitrary number of friendly walkers can share the same lattice sites. It is shown that a natural model describing the behavior of friendly walkers is an integrable model of the boson type. A representation of the generating function for the number of the lattice paths performed by a fixed number of friendly walkers for a certain number of steps is obtained. Bibliography: 22 titles. __________ Translated from Zapiski Nauchnykh Seminarov POMI, Vol. 335, 2006, pp. 59–74.     

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.     

Relaxing local modes and the theory of low-frequency Raman scattering in glasses

Raman scattering in glasses is investigated theoretically. The experimental Raman spectra of glasses exhibit a low-frequency peak (at ～10 cm^?1) that, as a rule, is attributed to vibrational modes of nanometer-sized structural units (nanocrystallites). It is established that the elastic moduli of nanocrystallites must necessarily be dependent on their sizes due to the Laplace pressure effect. A theory of the low-frequency peak is constructed using a realistic size distribution function of nanocrystallites with allowance made for the Laplace pressure effect and the dissipation of vibrational energy. Within this theory, the shape of the low-frequency peak and its evolution with temperature can be analyzed quantitatively. The proposed approach offers a physical interpretation of the experimental data and provides insight into the relation of the characteristic nanocrystallite sizes to the elastic moduli and surface tension coefficients of materials.