Browsing by Author "Cavaye, H."

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    Nitration of primary amines to form primary nitramines (Review)
    (2016-07-04) McAteer, Daniel; Pons, Jean-François; Wilson, I. I.; Cavaye, H.
    The nitration of primary amines to form primary nitramines is a rarely reported synthetic procedure which proceeds through a minimum of two steps. This is in stark contrast to the nitration of alcohols and secondary amines which is readily achievable by a number of methods in a single step. In general the primary amine must initially be activated to nitration as direct exposure to nitrating media tends to result in the formation of an ionic nitrate salt. This activation may be achieved through the use of a multitude of protecting groups that are stable to the nitrating conditions used thereafter. The review presented here is an attempt to bring together the published literature on this often overlooked synthetic procedure in energetic materials chemistry.
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    Primary alkyl phosphine-borane polymers: Synthesis, low glass transition temperature, and a predictive capability thereof
    (American Chemical Society, 2017-11-30) Cavaye, H.; Clegg, F.; Gould, P. J.; Ladyman, Melissa K.; Temple, Tracey J.; Dossi, E.
    With a multitude of potential applications, poly(phosphine-borane)s are an interesting class of polymer comprising main-group elements within the inorganic polymer backbone. A new family of primary alkyl phosphine-borane polymers was synthesised by a solvent-free rhodium catalysed dehydrocoupling reaction and characterised by conventional chemico-physical techniques. The thermal stability of the polymers is strongly affected by the size and shape of the alkyl side chain with longer substituents imparting greater stability. The polymers show substantial stability towards UV illumination and immersion in water however they undergo a loss of alkyl phosphine units during thermal degradation. The polymers exhibit glass transition temperatures (Tg) as low as -70 °C. A group interaction model (GIM) framework was developed to allow the semi-quantitative prediction of Tg values and the properties of the materials in this study were used to validate the model.