Co-precipitation in some binary sulphate systems

Studies have been made of the distribution behaviour of tracers with alkaline earth sulphates, using the technique of precipitation from homogeneous solution. The co-precipitation of strontium with barium sulphate and of lead, lanthanum, and yttrium, separately, with barium sulphate, and with strontium sulphate, were investigated. Although there was qualitative correlation between the observed values of the distribution coefficient and the theoretical solubility product ratios for each of the binary systems studied, the divergence between theory and observation was so great that it seems unlikely that there is any quantitative correlation.     

Synthesis of substituted 5-aminomethyl tetrahydro-isoquinolines and dihydro-isoindoles

The synthesis of ten substituted aminomethylene tetrahydro-isoquinolines is described, proceeding in eight steps from 5-hydroxyisoquinoline via reductive amination of N-Boc tetrahydro-isoquinoline 5-carboxaldehyde. Likewise, reductive amination was used to prepare four substituted dihydro-isoindoles from the corresponding aldehyde. The dihydro-isoindole ring system was conveniently accessed via a 2+2+2 cycloaddition reaction.     

Radical copolymerization of 2-acryloyl thioxanthone with methyl methacrylate

A novel monomer, 2-acryloyl thioxanthone (TXA), was prepared by reaction of 2-hydroxy thioxanthone with acryloyl chloride. Copolymerization of TXA with methyl methacrylate (MMA) in DMF at 80°C was studied in order to evaluate relative reactivities of these monomers. Values of 1.36 and 0.5 were found for the respective reactivity ratios of MMA and TXA, respectively. The resonance stabilization and polar properties were determined and discussed in terms of spectroscopic data.     

Photoinitiators for UV and visible curing of coatings: Mechanisms and properties

The radiation curing industry is one of the most rapidly developing fields in the entire coatings industry. The low toxicity, cheapness, speed, control and ease of formulation and operation are some of the main advantages of this growing technology. UV and/or visible light radiation is used to induce photochemical polymerization or crosslinking of a monomer, oligomer or prepolymer formulation containing a certain type of unsaturation, such as an acrylic group, and an appropriate initiator. The latter is used to absorb the light energy and transform it into active species, such as radicals or ions, capable of inducing such reactions. Applications extend to general coatings for paper, board, wood, tapes, compact discs and holograms, inks, photoresists for imaging processes and adhesives for welding and sealing in electronic circuit boards. The photoinitiator is the key to the control of these processes and, in recent years, has seen many new developments. These include the need for water-soluble, co-reactive and polymeric structures with low migration rates, as well as cheaper UV/ visible sensitizers with enhanced speed. New and effective cationic systems are also on the scene and, although expensive, are attracting significant academic and commercial interest.     

The observation of a large gauche preference when 2-fluoroethylamine and 2-fluoroethanol become protonated

The energies of the gauche and anti conformers of 2-fluoroethylamine, 2-fluoroethanol and their protonated analogues are calculated using density functional theory. Unlike the non protonated systems, the protonated systems show a strong gauche effect where the C-F and the C-(+)NH(3) or C-F and C-(+)OH(2) bonds are gauche rather than anti to each other. Single crystal X-ray diffraction studies of 2-fluoroethylammonium compounds identify the same conformational preference.     

Ab initio MO-SCF calculation on a model of anomalous water

Ab initio calculations are carried out on the planar hexamer model of anomalous water using a variety of basis sets. The results are compared to results of similar calculations on free water and water in the ice I-like puckered ring configurations.

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Zusammenfassung Es werden ab initio-Rechnungen für das planare Hexamer-Modell von anomalem Wasser unter Verwendung mehrerer BasissÄtze durchgeführt. Die Ergebnisse werden mit Resultaten Ähnlicher Rechnungen über freies Wasser und Wasser in der I-Eis Ähnlichen Konfiguration verzerrter Ringe verglichen.

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Résumé Calculs ab initio sur le modèle hexamérique plan de l'eau anormale en utilisant différentes bases. Les résultats sont comparés à ceux de calculs similaires sur l'eau libre et sur l'eau dans une configuration cyclique compacte analogue à celle de la glace I.

     

Photo-stabilising action of metal chelates in polypropylene—Part I: Excited state quenching versus UV antioxidant action under polychromatic irradiation

The photo-stabilising action of three metal chelates—nickel (II) 2,2′ thiobis (4-tert-octylphenylato) n-butylamine and the nickel and calcium derivatives of bis (ethyl-3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, in polypropylene—is examined using normal and second order derivative ultraviolet, infra-red and phosphorescence spectroscopic techniques and hydroperoxide analysis. Whilst all three stabilisers quenched the phosphorescence emission of a powerful photo-sensitiser, benzophenone, there was no protective action during photo-sensitised oxidation of the polymer. In the case of anthraquinone, there was no quenching and no protection. Processing history plays a dominant rôle in controlling the photo-stabilising performance of the chelates. Each stabiliser operates differently, being dependent on its relative stability during processing and photo-oxidation and on the formation and destruction of polymeric and antioxidant hydroperoxides during processing. Metal chelates operate by inhibiting polymer hydroperoxide formation during processing and acting as ultraviolet stable chain terminators or by giving products during the early stages of photo-oxidation which are themselves effective stabilisers.