Polymer science has developed new synthetic methods to create complex polymer architectures. The solution and bulk properties of these architectures are influenced by the structure and chemical composition of the original building blocks (e.g. monomers or reactive polymeric blocks). One of the greatest challenges to the field is characterization of these polymers with diverse structures and chemical compositions. Size exclusion chromatography (SEC) has been one of the most used characterization techniques to determine the molecular weight distribution (MWD) of polymers. The information obtained about the polymer from SEC is generally restricted to molecular weight averages and dispersity indexes. However, there is a wealth of valuable information that can be obtained from a deeper analysis of the SEC chromatograms. This information can provide insights into polymerization mechanisms, the amount of unreacted polymer in a coupling reaction, or even the amount of cyclic polymer formed during a ring-closure reaction.The thesis first develops the theory to analyse the SEC chromatograms and provides a methodology to fit the MWDs with a log-normal distribution (LND) model based on a Gaussian function. The LND model was then used to analyse polymers made by a variant of copper-mediated ‗living' radical polymerization (LRP) in water. This LRP technique is capable of producing hydrophilic polymers with both narrow MWDs and high chain-end functionality, but the chain-end halide groups were susceptible to hydrolysis upon purification attempts and, therefore, the polymers cannot be further used to create complex polymer architectures. To preserve high chain-end functionality, the terminal halide of the polymers was capped using in situ azidation at the end of aqueous coppermediated LRP. The azide chain-end fidelity of the purified polymer was tested in a coppercatalyzed azide-alkyne cycloaddition (CuAAC) ‗click' reaction. The LND model of MWDs of the resulting products gave an accurate determination of the end-group functionality and insight into the effectiveness of our new polymerization variant.In the final stage of this thesis, the LND model was used to quantify the sequential polymerization of cyclic macromers through successive CuAAC ‗click' reactions. The versatility of the LND model was further demonstrated by determining the multicyclic coil conformation as a function of the number of cyclic macromers in the polymer chain.iii
Declaration by authorThis thesis is composed of my original work, and contains no material previously published or written by another person except where due reference has been made in the text. I have clearly stated the contribution by others to jointly-authored works that I have included in my thesis.I have clearly stated the contribution of others to my thesis as a whole, including statistical assistance, survey design, data analysis, significant technical procedures, professional editorial advice, and any other original research work used or reported in my thesis. The content of my ...