The effect of organic nitriles on the radiation induced polymerization of styrene

The effect of a range of 10 organic nitriles on the radiation-induced polymerization of styrene was studied. A dose rate of 4.4 rad s^?1 was used. A rate of polymerization of styrene (1.744 mol L^?1 of toluene solution) of 5.0 × 10^?7 mol L^?1 s^?1 was found. With organic nitriles present (styrene:nitrile ratio of 1:0.28) the rate of polymerization increased. Rates in the range of 5.5 × 10^?7 ?5.2 × 10^?6 mol L^?1 s^?1, depending on the nitrile present, were obtained. The polymers were partially characterized and evidence of involvement of each of the nitriles in the polymer chains was revealed. The increase in rate of polymerization has been attributed to the part played by nitrile radicals in the initiation of styrene polymerization. Radical yield values [as G(nitrile radical)] were derived from the relevant rate expressions. Values ranged from 2.7 to 49.5, depending on the particular nitrile. Corresponding values of G(nitrile radical) in the range of 5.1–129.4 were obtained by the manipulation of number-average molar mass data. Values of k_pk_t of approximately 2 × 10^?5 L mol^?1 s^?1 were found. Trommsdorff types of effect are absent from these systems.     

Nature of mechanically induced defects in polycrystalline hydrargillite and Al2O3-A1(OH)3 studied by radiation methods

Mechanical treatment of hydrargillite Al(OH)₃ in a vibrational grinder and in a ball-mill grinder increases the dispersion, the specific surface area, and the unit-cell constants. An x-ray amorphous phase forms. Differences in the nature and in the concentration of paramagnetic centers arise on irradiation (77 K) of the mechanically treated samples. Anion vacancies and oxygen ions with disrupted short-range order appear in the mechanically treated samples. Their concentration increases with increased time of mechanical treatment. Pulsed thermal treatment of hydrargillite forms the Al₂O₃-Al(OH)₃ system and anneals the mechanically induced defects.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1463–1467, July, 1990.     

The molecular structure of tetrathiofulvalene-13C (TTF) from proton magnetic resonance studies using nematic solvents

The molecular structure of TTF dissolved in nematic liquid crystalline solvents has been determined from the proton magnetic resonance including couplings due to ¹³C in natural abundance. The molecule is puckered in a boat conformation with the SCHCHS planes making a dihedral angle of 13 ± 2° with the S₂C  CS₂ plane. The other structural parameters obtained are r_CH = 1.085 ± 0.014 Å and the angel CCH = 123.7 ± 1.5°.     

Effect of syndiotacticity on the aqueous poly(vinyl alcohol) gel 3. Mechanical property of gel

Summary The mechanical property of aqueous gel was studied using the PVA having the content of syndiotacticity in diad from 58.4 and 66.2%. The elastic modulus of gels was 105–106 dyne/cm2 and the variation of the elastic modulus of gel with the rise of temperature was corresponded with the variation of the concentration of PVA in gel accompanying syneresis. The elastic modulus of gel having the same content of syndiotacticity and concentration of PVA increased in the order as follows, the first is the gel chilled at room temperature, the second is the gel chilled at 60 °C and last is the gel chilled at 0 °C. The variation of the elastic modulus of gel with the rise of temperature became smaller with increasing content of syndiotacticity. The increase of elastic modulus is considered to be attributed to the further growth of stronger junctions through the recrystallization followed by syneresis rather than the entropic effect of polymer networks with the rise of temperature.

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Zusammenfassung Es wurden die mechanischen Eigenschaften wßriger Gele aus Polyvinylalkohol untersucht, mit Gehalten an Syndioaktizität in Diaden zwischen 58,4 und 66,2%. Die elastischen Moduln der Gele lagen bei 105 bis 106 dyn/cm2 und die Variation der elastischen Moduln der Gele mit Steigerung der Temperatur entsprach der Konzentrationsänderung von Polyvinylalkohol im Gele gemäß der stattgefundenen Synärese. Der elastische Modul des Gels mit konstantem Gehalt an Syndiotaktizität und Konzentration des PVA steigen in folgender Weise: Zuerst das Gel abgekühlt bei Raumtemperatur, dann das Gel abgekühlt bei 60 °C und zuletzt das Gel erstarrt bei 0 °C. Die Variation der elastischen Moduln mit steigender Temperatur wird kleiner mit steigendem Gehalt an Syndiotaktizität. Das Anwachsen der Moduln sollte vermutlich dem weiteren Wachstum strengerer Kopp lungen durch Rekristallisation infolge der Synärese zuzuschreiben sein mehr als einem Entropieeffekt der polymeren Netzwerke mit steigender Temperatur.

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With 6 figures and 2 tables

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Part 2. cf. reference 2.     

Application of ESCA to polymer chemistry. VIII. Surface structures of AB block copolymers of polydimethylsiloxane and polystyrene

The surface morphology of a number of films of AB block copolymers of polydimethylsiloxane and polystyrene was examined by ESCA and contact angle measurements. In all cases the immediate surface is shown to consist of an essentially pure polydimethylsiloxane component. By comparing the intensities of elastic peaks corresponding to photoionizations from core levels without energy loss for polydimethylsiloxane and polystyrene with those for the block copolymers and by consideration of shake-up phenomena specific to the polystyrene component, an estimate of the thickness of the polydimethylsiloxane outer layer of the latter may be obtained. This is shown to vary between ～13 and 40 Å, depending on the method of formation of copolymer film.     

Phosphorus in organic synthesis—VII : Diphenyl phosphorazidate (DPPA). A new convenient reagent for a modified curtius reaction

A simple one-step conversion of carboxylic acids to urethanes was achieved by diphenyl phosphorazidate (DPPA). The reaction procedure is quite simple, occurring by refluxing an equimolecular mixture of a carboxylic acid, DPPA, and triethylamine in the presence of a hydroxyl component. Aromatic, aliphatic, and heterocyclic carboxylic acids underwent rearrangements in satisfactory yields. As this modified Curtins reaction is much simpler and less laborious than the classical Curtius reaction and proceeds under mild conditions, it may have a broad synthetic utility.     

Instrumental neutron activation determination of Pt, Ru, Ir, Sc, Cr, Fe, Co, La, Ce, Nd, Sm, Yb, Lu, Hf and Ta employing CIRUS reactor as a thermal neutron source

An accurate and simple method has been developed for the determination of Pt, Ru, Ir and other elements employing instrumental neutron activation analysis (INAA). Nondestructive analysis has been carried out for the determination of these elements in different rock samples such as Dolerite, Dyke Dolerite, Country Basalt, Hyaloclastite, Trachyte, Ijolite, Spillite, Diorite and Lamprophyre from various locations like Daman, Tapti, Murud, Talasari, Ranala and Bassein in Maharashtra state. High flux provided by the CIRUS reactor (1×10¹³ n cm^–2s^–1) has been used for thermal neutron bombardment followed by radioassaying of the (n,) products on a HPGe detector coupled to a PC-based MCA unit.     

6(5H)-phenanthridinones. II. Preparation of substituted 6(5h)-phenanthridinones from 9-oxofluorenes

A number of 6(5H)-phenanthridinones have been conveniently prepared from 9-oxofluorenes through the Schmidt reaction. It has been found that all amino and nitro 9-oxofluorenes thus far tried gave substituted 6(5H)-phenanthridinones with the amino or nitro group situated in the benzene ring attached to the nitrogen of the lactam group. UV and IR spectral data are presented for these compounds.     

Pharmacologically interesting compounds—I: High resolution mass spectra of phenothiazines

The mass spectra of twenty-six commercially available medicinal phenothiazines have been determined at high resolution. In each compound, the side chain attached to the 10-position of the phenothiazine ring contains nitrogen and fission of the C? C bond α to this nitrogen gives in most cases the base peak. Some of the compounds are also substituted at the 2-position and this substituent generally remains intact, though some substituents such as acetyl, propionyl, methoxyl and methylthio can undergo fragmentation. Fragmentations fall into three groups; those which give ions representing a part of the side chain; those which give ions representing the intact phenothiazine ring with part of the side chain attached; those which give ions representing a partially fragmented ring system.