Structure Development in Simple Cross-Linked Organopolysiloxanes

13C CP and CPPI MAS NMR have been carried out on thermally cured samples of polymethylvinylsiloxane and polydimethylsiloxane. By varying the CP contact time, the and vinyl carbons and the methyl carbon of the CH3–(SiO<)–CH=CH2 species could be identified. A further methyl carbon was detected which was less mobile and which we assign to methyl groups attached to silicon species on which the vinyl group has reacted to form a cross-link. Resonance from – CH2– carbons was observed in the 30–40 ppm range, and these species arise from methyl-vinyl cross-linking to give CH3–(SiO<)– H2– H2–(SiO<)–CH=CH2. Higher temperature curing promotes vinyl-vinyl cross-linking to give CH3–(SiO<)–CH2– H–CH2–(SiO<)–CH3 links between chains. Evidence for this comes from the insensitivity of the carbon resonance under CPPI, indicating that it is in a – CH= rather than a =CH2 environment. There was also evidence of –CH2– carbons in the polydimethylsiloxane material, suggesting that thermally activated, methyl-methyl cross-linking can occur to give CH3–(SiO<)– H2– H2(SiO<)–CH3 links between chains.     

O-H ... O(S) hydrogen bonds in 2-hydroxy(thio)benzamides. Survey of spectroscopic and structural data

Summary From a survey of spectroscopic and structural data of six corresponding 2-hydroxybenzamides and 2-hydroxythiobenzamides (amide, N-methylamide, N,N-dimethylamide, piperidide, morpholide, 2,6-dimethylpiperidide) remarkable similarities between O(N)-H ... O and O(N)-H ... S hydrogen-bonds are obtained, concerning both, hydrogen-bond patterns and hydrogen-bond strengths. In dilute solution the OH groups of all compounds are intramolecularly associated to the (thio)carbonyl O (S) atoms with distinctly larger hydrogen-bond strengths for primary and secondary amides [ (O-H)=2950–3020 cm^–1, (OH)=12.16–11.99 ppm] and thioamides [ (O-H)=2960–3000 cm^–1, (OH)=11.65–11.13 ppm], than for tertiary amides [ (O-H)=3200–3250 cm^–1, (OH)=9.95–8.95 ppm] and thioamides [ (O-H)=3245–3330 cm^–1, (OH)=8.09–7.06 ppm]. In the solid state, the OH groups of the primary and secondary (thio)amides are also engaged in rather strong intramolecular O-H ... O=C [O ... O=2.51 Å, (O-H)=2700–2750 cm^–1] and O-H ... S=C [O ... S=2.90–2.94 Å, (O-H)=2700–2840 cm^–1] hydrogen-bonds; thetrans-NH groups of the primary (thio)amides and the NH groups of the secondary (thio)amides connect the molecules to N-H ... O-H [N ... O=2.93–3.10 Å, (N-H)=3319–3407 cm^–1] hydrogen-bonded chains; the remainingcis-NH groups of the primary (thio)amides give rise to eight-membered cyclic dimers via N-H ... O=C [N ... O=2.93 Å, (N-H)=3226 cm^–1] and N-H ... S=C [N ... S=3.46–3.47 Å, (N-H)=3233–3277 cm^–1] hydrogen-bonds. Contrary, the OH groups of the tertiary (thio)amides are intermolecular associated in the solid state and link the molecules to O-H ... O=C [O ... O=2.63–2.75 Å, (O-H)=3075–3135 cm^–1] and O-H ... S=C [O ... S=3.18–3.26 Å, (O-H)=3130–3190 cm^–1] hydrogen-bonded chains.

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O-H ... O(S)-Wasserstoffbrückenbindungen in 2-Hydroxy(thio)benzamiden. Ein Überblick über spektroskopische und strukturelle Daten

Zusammenfassung Aus einer Zusammenstellung von spektroskopischen und strukturellen Daten von sechs entsprechenden 2-Hydroxybenzamiden und 2-Hydroxythiobenzamiden (Amid, N-Methylamid, N,N-Dimethylamid, Piperidid, Morpholid, 2,6-Dimethylpiperidid) ergeben sich bemerkenswerte Analogien zwischen O(N)-H ... O und O(N)-H ... S H-Brücken, die sowohl die H-Brücken-Muster als auch die H-Brücken-Stärken betreffen. In verdünnter Lösung sind die OH-Gruppen aller Verbindungen intramolekular mit den O(S)-Atomen der (Thio)Carbonylgruppen assoziiert, wobei die H-Brücken bei den primären und sekundären Amiden [ (O-H)=2950–3020 cm^–1, (OH)=12.16–11.99 ppm] und Thioamiden [ (O-H)=2960–3060 cm^–1, (OH)=11.65–11.13 ppm] deutlich stärker sind, als bei den tertiären Amiden [ (O-H)=3200–3250 cm^–1, (OH)=9.95–8.95 ppm] und Thioamiden [ (O-H)=3245–3330 cm^–1, (OH)=8.09–7.06 ppm]. Im Festkörper weisen die primären und sekundären (Thio)Amide ebenfalls sehr starke intramolekulare O-H ... O=C [O ... O=2.51 Å, (O-H)=2700–2750 cm^–1] und O-H ... S=C [O ... S=2.90–2.94 Å, (O-H)=2700–2840 cm^–1] H-Brücken auf; dietrans-NH-Gruppen der primären (Thio)Amide und die NH-Gruppen der sekundären (Thio)Amide verknüpfen die Moleküle über N-H ... O-H H-Brücken [N ... O=2.93–3.10 Å, (N-H)=3318–3407 cm^–1] zu Ketten; die verbleibendencis-NH-Gruppen der primären (Thio)Amide bilden zyklische, über N-H ... O=C [N ... O=2.93 Å, (N-H)=3226 cm^–1] und N-H ... S=C [N ... S=3.46–3.47 Å, (N-H)=3233–3277 cm^–1] H-Brücken gebundene, 8-Ring-Dimere. Im Gegensatz dazu sind die OH-Gruppen der tertiären (Thio)Amide im Festkörper intermolekular assoziiert und verknüpfen die Moleküle über O-H ... O=C [O ... O=2.63–2.75 Å, (O-H)=3075–3135 cm^–1] und O-H ... S=C [O ... S=3.18–3.26 Å, (O-H)=3130–3190 cm^–1] H-Brücken zu Ketten.

     

Radiolytic gas formation under γ-irradiation of oxalic acid solutions

Radiolytic gas formation under -irradiation (10⁴–10⁶ Gy) of 10^–2–10^–4 M aqueous solutions of oxalic acid at 25–60°C was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 11, 2004, pp. 1836–1839.Original Russian Text Copyright © 2004 by Popova, Voronin, Byvsheva.     

Study on the Melting Process of Nitrocellulose by Thermal Analysis Method

The melting process of NC is studied by using modulated differential scanning calorimetry (MDSC) technique, the microscope carrier method for measuring the melting point and the simultaneous device of the solid reaction cell in situ/RSFT-IR. The results show that the endothermic process in the MDSC curve is reversible. It is caused by the phase change from solid to liquid of the mixture of initial NC, decomposition partly into condensed phase products. The values of the melting point, melting enthalpy (H_m), melting entropy (S_m), the enthalpy of decomposition (H_dec) and the heat-temperature quotient (S_dec) obtained by the MDSC curve of NC at a heating rate of 10 K min^–1 are 476.84 K, 205.6 J g^–1, 0.4312 J g^–1 K^–1, –2475.0 J g^–1 and –5.242 Jg^–1K^–1, respectively. The MDSC results of NC with different nitrogen contents show that with increasing the nitrogen content in NC, the absolute values of H_m, S_m, H_dec and S_dec increase.This revised version was published online in November 2005 with corrections to the Cover Date.     

Preparation of ultradispersed transition metals in immobilized microreactors

Preparation of ultradispersed transition metals (20–100 nm) by reduction of metal complexes in molecular microreactors (cavities of immobilized calixarenes, polyelectrolytes) was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 11, 2004, pp. 1914–1916.Original Russian Text Copyright © 2004 by Altshuler, Sapozhnikova.     

Group additivity for the standard partial molal heat capacities and volumes of polar compounds in methanol at 25°C

A flow heat capcity calorimeter and a flow vibrating tube densimeter have been used to measure the apparent molal heat capacities and volumes of benzene and 25 polar compounds in methanol at 25°C. These quantities have been extrapolated to infinite dilution to obtain the standard partial molal heat capacities and volumes. The and data have been used in conjunction with an additivity scheme previously determined for alkanes. Group contributions were evaluatd for –OH, –NH₂, –COOH, –C₆H₅, C=O, –COO–, –CONH–, –O–, –S–, and –S₂–. The concentration dependences of _cp and _v of nonelectrolytes in methanol are qualitatively similar but much smaller than in water.     

Features of oxidation of titanium group metals in air

The kinetics and mechanism of oxidation of titanium, zirconium, and hafnium in air at 973–1473 K were studied in relation to the properties of the metals.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1409–1415.Original Russian Text Copyright © 2004 by Dyachkov.     

Phase and chemical transformations of lanthanum and iron alloys in a nitrogen-hydrogen medium

The behavior of La_xFe_1–x alloys in a nitrogen-hydrogen medium at 293–723 K and a pressure of up to 1.5 × 10⁷ Pa was studied. The alloys decompose to give LaH_2.9 and -Fe at 293 K, LaN, LaH_2.4, and -Fe at 623 K, and LaN and -Fe at 723 K. Ammonia was detected in the gas phase at 623–723 K.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1241–1243.Original Russian Text Copyright © 2004 by Shilkin.This revised version was published online in April 2005 with a corrected cover date.     

Variation of the parameters of inhibited oxidation of polyethylene in the region of phase transition

Parameters of oxidation of polyethylene with molecular oxygen in the presence of a phenolic antioxidant, 2,2-methylenebis(4-methyl-6-methylcyclohexylphenol), at 80–210°C were studied. The possible mechanism of interaction of the polymer with the antioxidant near the melting point was considered theoretically. The suggested theoretical relationships are consistent with experimental data.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1378–1381.Original Russian Text Copyright © 2004 by Shlyapnikov, Kolesnikova.     

Thermal reactions of dialkyl disulfides with acetylene in the presence of methanol

Gas-phase reaction of diethyl disulfide or disulfide oil with acetylene performed in the presence of methanol provides an essentially more selective thiophene formation. The yield of thiophene increases by 20–30%, and the yield of by-products decreases by half.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1318–1320.Original Russian Text Copyright © 2004 by Deryagina, Sukhomazova, Levanova, Korchevin, Russavskaya.This revised version was published online in April 2005 with a corrected cover date.     

Thermodynamic study of adsorption of nickel complexes with Schiff bases from acetonitrile solutions on uncharged graphite surface

Adsorption of nickel N,N-ethylenebis(salicylideneimine) complex from acetonitrile solution on expanded natural graphite powder at 273–313 K is studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 10, 2004, pp. 1643–1646.Original Russian Text Copyright © 2004 by Afanasev, Aleksandrova, Akulova, Logvinov.     

IR spectroscopic study of the conformational lability of 4′-ethyl-4-cyanobiphenyl

The conformational lability of 4-ethyl-4-cyanobiphenyl molecules in solid crystal (SC) and isotropic liquid (IL) states was investigated by IR spectroscopic techniques (experiment and theory). IR absorption spectra were measured at 28°C–95°C in the frequency range 400 cm^–1–4000 cm^–1. Spectrum simulation was performed using the fragment method with allowance for the conformational fluctuations of molecules. The experimental and calculated spectra were compared and analyzed, and it was shown that in the IL, the samples are mixtures of conformers. The temperature changes in the spectra in the stated range are caused by the conformational lability of molecules.Original Russian Text Copyright © 2004 by L. M. Babkov, I. I. Gnatyuk, G. A. Puchkovskaya, and S. V. TrukhachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 398–405, May–June, 2004.     

Vibrational spectra of 2-biphenylmethanol. Spectrum simulation and molecular structure

The vibrational spectra of a solid crystalline sample of 2-biphenylmethanol have been measured at room temperature. The IR absorption spectra were recorded in the range 400 cm^–1–3600 cm^–1; Raman spectra were measured in the range 10 cm^–1–1640 cm^–1. The direct mechanical and optoelectronic problems were solved using the fragment method realized as Lev-100 software; the intensity distribution in the IR spectrum of 2-biphenylmethanol was obtained by the same method. The experimental Raman and IR absorption spectra were interpreted by analyzing the calculated data on the frequencies and forms of normal vibrations and their intensities in the IR spectra. IR absorption spectra were simulated for several models of 2-biphenylmethanol conformers that differ in the mutual orientation of fragments. Based on the results of simulation and comparison of the calculated and experimental spectra of conformers we suggested a model for the conformer realized in the solid phase under normal conditions.Original Russian Text Copyright © 2004 by L. M. Babkov, J. Baran, N. A. Davydova, J. I. Kukielskii, and S. V. TrukhachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 624–631, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Distribution of natural radionuclides

The distribution of natural nuclides and of the effective specific radioactivity in processing of the sphene concentrate was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1237–1240.Original Russian Text Copyright © 2004 by Melnik, Lokshin, Sedneva.     

Influence of copper stearate on oxidation of polyethylene stabilized with Neozon D

Catalytic reaction of copper(II) stearate with Neozon D in a polyethylene melt was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1539–1542.Original Russian Text Copyright © 2004 by Lin, Vorobeva, Marchenko.     

Mechanical activation of aluminum: 2. Size,shape, and structure of particles

The structure of active Al/C composite prepared by the mechanochemical method from aluminum and graphite powders (10–30 wt % C) is studied by scanning and transmission electron microscopies, atomic force microscopy, local elemental analysis, X-ray diffraction, as well as by adsorption and sedimentation measurements. It is established that the particles of chemically active Al/C composite represent porous plate-like aggregates with a mean size smaller than 2.5–5 m and composed of nanocrystalline aluminum blocks with a size of 15–60 nm distributed in a loose amorphous carbon. Single aluminum particles with a size of up to 10 nm are also observed; however, their weight fraction is small.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 819–828.Original Russian Text Copyright © 2004 by Streletskii, Pivkina, Kolbanev, Borunova, Leipunskii, Pshechenkov, Lomaeva, Polunina, Frolov, Butyagin.     

Air electrode of chemical power cell as oxygen sensor

The possibility of using the air electrode of a chemical power cell as an electrochemical oxygen sensor was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 10, 2004, pp. 1663–1666.Original Russian Text Copyright © 2004 by Danilov, Kolbasov, Vyunova.     

Thermolysis of hexachlorocyclohexane in a flow-through packed reactor

Thermolysis of hexachlorocyclohexane in a flow-through packed system in an inert gas atmosphere was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1528–1532.Original Russian Text Copyright © 2004 by Kutin, Gubanova, Zorin, Zanozina, Markova, Suprunova, Bykova.     

The first ionization constant from 25 to 200°C and 2000 bar for orthophosphoric acid

The ionization constant of orthophosphoric acid, determined by conductivity measurements, decreased from 7.11×10^–3 at 25°C to 6.2×10^–4 mol-kg^–1 at 200°C. The pressure effect to 2000 bar was also measured and the ratio K₂₀₀₀/K₁ is 2.7 at 25°C and 3.7 at 200°C. The standard partial molar volume change for the ionization at 1 bar, , changes from –16.1 at 25°C to –33.3 cm³-mol^–1 at 200°C. The partial molar compressibility change for the ionization, , varies from –3.8×10^–3 to –8.3×10^–3 cm³-mol^–1 bar^–1 over the same temperature range.     

IR study of cation effects on the O-D stretching frequencies of isotopically dilute HDO in aqueous salt solutions

IR spectra of 3 normal solutions of 14 different salts [chlorides of Al⁺⁺⁺, Be⁺⁺, Mg⁺⁺, Ca⁺⁺, Sr⁺⁺, Ba⁺⁺, Zn⁺⁺, Cd⁺⁺, Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, N(CH₃) ₄ ⁺ ] in both, 96% H₂O+4% D₂O and 100% H₂O, were measured in the frequency range =2 800–2 100 cm^–1. From up to 18 single measurements for each solution the frequencies and halfwidths of the O-D stretching bands of isotopically dilute HDO were determined with high accuracy. Frequencies in the range =2 510–2 529 cm^–1 and halfwidths in the range =155–205 cm^–1 resulted atT=30°C with standard deviations typical less than ±1 cm^–1 and ±4 cm^–1, respectively. An almost perfect correlation between the O-D stretching band parameters and the polarizing power of the cations was obtained.Herrn Prof. Dr.A. Neckel, Wien, zum 60. Geburtstag gewidmet.