Date of Award

Spring 2012

Degree Type

Thesis

Degree Name

Doctor of Philosophy (PhD)

Department

Chemical Engineering

Supervisor

David K. Potter

Language

English

Abstract

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.

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