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Biodegradable polyesters are considered as one of the most cost effective and environmentally friendly solutions to waste-disposal problems associated with traditional thermoplastics. The technologies for converting the resins into useful items require knowledge about the rheological properties of these materials. Adequate rheological models are essential for the design and optimization of the process technologies. Rheological properties of two commercial biodegradable polyesters- poly(lactic acid) (PLA) and aliphatic-aromatic co-polyester (AAC) Ecoflex -have been investigated using parallel plate and capillary rheometers. Results from a study on the extrusion instabilities of biodegradable polymers are reported for the first time. The experimental studies found that the biodegradable polyesters exhibit pseudoplastic (shear-thinning) behaviour and the Cox-Merz rule is obeyed. A Cross model was proposed to describe their shear-thinning behaviour. The viscosity of both PLA grades is more temperature sensitive than the viscosity of Ecoflex. It was observed that the extensional viscosity of Ecoflex is larger than that of PLA and that the extensional viscosity of biodegradable polymers is similar to that of LLDPE. The experimental results indicate that biodegradable polymer melts slip at the die wall. It was observed that with increasing shear rate PLA exhibits sharkskin and gross melt fracture while Ecoflex exhibits only gross melt fracture. With regards to flow instabilities PLA behaves like linear polyolefins, however without exhibiting stick-spurt phenomenon. While Ecoflex behaves like branched LDPE, its gross melt fracture starts at higher values of wall shear stress than LDPE. Both biodegradable materials exhibit small extrudate swell: up to 28% for PLA and up to 34% for Ecoflex, which is comparable to that of rigid PVC. It was observed that biodegradable polymers substantially degrade during extrusion processing. It was also found that blending PLA and Ecoflex produced immiscible blends. Melts of these blends exhibited sharkskin and gross melt fracture at higher shear stresses than the neat resins. This effect was attributed both to degradation during blending and to some sort of lubricating effect. / Thesis / Master of Applied Science (MASc)

Rheological modification is frequently cited as a key application for hyperbranched polymers. However, the high degree of branching in these polymers restricts entanglement and the resultant mechanical properties suffer. Longer distances between branch points may allow entanglements. Highly branched polymers, where linear units are incorporated between branch points, are synthesized with an oligomeric A2 plus a monomeric B3. Higly branched polymers differ from traditional hyperbranched polymers in that every monomeric repeating unit of a hyperbranched polymer is a potential branch point, which is not true for highly branched polymers. The oligomeric A2 plus B3 synthetic methodology was used for the synthesis of highly branched ionenes and polyurethanes. Highly branched ionenes, which have a quaternary ammonium salt in the main chain, were synthesized with a modified Menshutkin reaction. The oligomeric A2 was comprised of well-defined telechelic tertiary amine endcapped poly(tetramethylene oxide). Reduced mechanical properties were observed for highly branched polymers compared to linear counterparts. Highly branched polyurethanes were synthesized with polyether soft segments including poly(ethylene glycol), poly(tetramethylene glycol), and poly(propylene glycol). Degree of branching was determined via a novel 13C NMR spectroscopy approach, which is described herein. The classical degree of branching was supplemented with an alternative degree of branching equation, which was tailored for highly branched architectures. The melt and solution viscosities of highly branched poly(ether urethane)s were orders of magnitude lower than the linear analogs. For the first time, the presence of entanglements was confirmed for highly branched polymers. Doping the highly branched polyurethane with lithium perchlorate, a metal salt, resulted in a significantly higher melt viscosity. The ionic conductivity of the highly branched polyurethane when doped with a metal salt was orders of magnitude higher than the linear analog. Soybean oil was oxidized for synthesis of soy-based polyol monomers. Three regimes were determined, and for the first time, a correlation between hydroxyl number and a resonance from the double bonds of soybean oil in 1H NMR spectroscopy was described. The relationship was used to accurately describe oxidation of soybean oil with time, temperature, and air flow rate. Soybean oil oxidation was catalyzed, and tack-free films were formed. / Ph. D.