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A 3-year-old child with tertiary trisomy 14 (+14q-), daughter of a mother with a balanced reciprocal translocation [46,XX,t(14;16) (q11;q24)] is presented. Craniostenosis and developmental retardation were the primary presenting features in this patient.

Low molecular weight functionalized polyolefins are mainly used as additives in adhesive formulations, compatibilizing agents and aqueous dispersions. However, the low viscosity and functionality they offer has never been explored to generate high molecular weight products that offer improved processing routes for polyolefins as well as wider applications. The aim of this thesis work was to investigate the preparation and characterization of thermoset material by reactions between a highly functionalized, low viscosity maleic anhydride grafted polyethylene and diamines. Reactions were performed both in solution and in the melt state to generate the target thermoset materials. Products from these reactions were extensively explored using different techniques to understand the reaction kinetics and mechanism. Thermosets generated were also characterized for the degree of crosslinking, thermal, mechanical and thermomechnical properties. Reactions in solution showed that the degree of reaction could be easily controlled by manipulating the concentration of reactants in the reaction mixture. Mixing torque data from the melt blender generated during reactions in the melt phase suggested that reaction between anhydride and amine moieties in these systems happen at much slower rate than widely reported for conventional high molecular weight polymeric systems. Unlike a single or two closely merged peaks in mixing torque associated with melting of polymer and chain extension and crosslinking due to reaction between anhydride and amine functionality widely reported, two separate peaks were observed in this study. A combination of FTIR and insoluble fraction data generated suggested that the first peak observed in mixing torque represents a combination of melting and partial reaction between anhydride and amine functionality. Whereas, the second peak in the mixing torque represents the initiation of crosslinking. The slower kinetics observed in the current investigation was found not to be a consequence of immiscibility of polyether diamine and polyethylene or the relatively higher molecular weight of diamines utilized in some reactions since using a low molecular weight aliphatic diamine, hexamethylenediamine, produced similar trends. FTIR and gel content (insoluble fraction) data generated on the prepolymers by processing them at high temperatures, suggested residual anhydride presence in products which could not be assessed using FTIR. This observation renders the popular monitoring of anhydride peak in such systems to assess the degree of reaction highly questionable. Cured thermosets from the prepolymers produced showed gel fractions of the same scale as in traditional crosslinked products. DSC heat scans on the thermosets showed separate crystal populations for polyethylene in cured and uncured fraction. Dynamic mechanical analysis result showed the thermosets withstood temperature up to 200 °C without failure and a crosslink plateau could be observed following the melting transition. Tensile properties of the thermosets were observed to be promising and composition dependent. These thermosets are expected to extend the polyolefins applications in areas like sealant, adhesive and coatings. The low viscosities of starting materials could also lead to new processing routes for polyolefins. Doctor of Philosophy (PhD)

Hot-melt adhesives have been commercially available for a long time and they are used in a wide range of applications. The adhesive performance is governed by the adhesive material property as well as the application conditions for each type of substrate. In order to achieve a good bond between the adhesive and the designated substrate, both wetting ability and open time of the adhesive material have to be considered. Three commercial hot-melts were used in this study in order to examine the relationship between the material property and the adhesive performance. The thermal properties of the materials were obtained through Differential Scanning Calorimetry while Dynamic Analysis (DA) described their viscoelastic behaviour, and the hysteresis loop helped to characterize the flow regime from which the application conditions for the adhesive could be chosen. The adhesive performance was evaluated in term of the force required to break the bond between the adhesive and the substrate through a series of standardized pull-off tests. The effect of the time-temperature trade-off on the adhesive performance by varying the application temperature as well as prolonging the available bond-formation time was also examined. In most cases, the adhesive performance improved with extended open time. However, improved adhesive performance was also shown to be the response of shorter Maxwell characteristic time which was evaluated from the DA data. By providing the characteristic time as a linkage, a relationship between the adhesive performance and the material properties could be established. These results also offer a basis for the formulation of adhesives using structure-property parameters derived from DA. Master of Applied Science (MASc)