Synthesis and Proprieties of Oligo(2-ethyl-2-oxazoline)-Based Polymers with Discrete Architecture

Dispersity within polymer brushes plays a major role in determining interfacial proprieties such as hydrophilicity, lubrication and interaction within proteins in biological media, thus critically influencing the performance of brush-functionalized surfaces and materials. In particular, side-chain dispersity in polymer brushes bearing functional oligomeric side chains can deeply influence their interfacial proprieties, due to the occurrence of solvophobic intermolecular polymer-polymer interactions. In recent years, the development of controlled radical polymerization (CRP) techniques, together with the possibility of synthesizing tailored macromonomers subsequently separated into discrete fractions through preparative chromatography, has led to the design of polymeric architectures with precisely defined structure. This thesis focuses on synthesizing a library of polymer brushes bearing polydisperse and discrete oligo(2-ethyl-2-oxazoline) (OEOXA) side chains with precisely defined number of 2-ethyl-2-oxazoline units. The discrete macromonomers employed for the synthesis of polymer brushes were obtained by purifying methacrylate-terminated OEOXAs by flash chromatography. The LCST behaviour of each polymer in solution was studied, to determine the influence of side-chain dispersity on hydration.