A series of new metal (M) dithiolene complexes bearing terthiophene (3, 12, M = Ni; 4, M = Pd; 5, 6, M = Au) and 2,5-bis(para-methoxyphenyl)thiophene units (14, M = Ni; 15, 16, M = Au; 17, M = Pd) have been synthesised in 38-99% yield. The electrochemical properties of the materials have been characterised by cyclic voltammetry and UV-vis spectroelectrochemistry. The nickel complexes possess low oxidation potentials (-0.12 to -0.25 V vs Ag/AgCl) due to the electron-rich dithiolene centres and all complexes display ligand-based redox activity. The terthiophene derivatives have been polymerised by electrochemical oxidation to give stable films with, in the case of poly(3), broad absorption characteristics. Charge transfer materials have been isolated from 14 and 16 with conductivities in the range 9 x 10(-6) to 7 x 10(-8) S cm(-1).
Polyurethane (PU) is one of the most versatile polymers available and can be found in an infinite number of formats ranging from rigid or flexible foams to elastomers. Currently, most Rigid PU Foam (RPUF) waste is landfilled, even though a small amount is mechanically recycled, in which the material is conditioned in size to a very fine powder, which is introduced as a filler. In this work, chemical recycling of two types of rigid PU foams is studied, the major difference being the aliphatic or aromatic nature of the isocyanate used in the synthesis. A solvolysis process is developed, a chemical depolymerization that breaks the chains by means of a chemical agent, a solvent, in the presence of a catalyst and under controlled process conditions. The glycolysis products are purified by vacuum distillation, centrifugation, and acid water treatment, depending on the most suitable process for each waste type. Optimal process conditions are established to obtain high-purity green polyols by performing a set of catalytic glycolysis reactions at laboratory scale with the previously conditioned RPUF waste samples. The physicochemical properties of the polyols, such as hydroxyl value, acid value, average molecular weight (Mn), and viscosity, are analyzed. The chemical structure and thermal stability of the polyols are studied by means of FTIR and TGA, respectively. Partial substitution of the commercial polyol (up to 15 wt.%) by the recycled polyols for RPUF synthesis is studied and characterized.
Traditional description of the rate of the thermoset resin reaction by the Arrhenius relationship multiplied by a reaction function has been used in this study. The Kissinger method and ASTM E 698 procedure have been used for a determination of parameters of the Arrhenius relationship. N-th order, Prout-Tompkins and Kamal-Sourour models have been used and evaluated as the reaction functions to formulate the curing kinetic models of an epoxy resin.An engineering tool based on Microsoft Excel code has been developed by using the developed methodology. This tool has been successfully applied for a building of the curing kinetic model of vinyl ester resin with high microwave absorption properties to be used in the microwave assisted pultrusion processes.
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