Atom Transfer Radical Polymerization of Polar Monomers and Synthesis of Block Copolymers for Industrial and Biomedical Applications

The aim of this thesis is to push forward the synthesis of well-defined materials containing polar monomers. The ATRP of polar monomers was investigated with the aim to obtain living and well-defined materials. Block copolymers with pre-determinable composition and unimodal distribution of molecular weight were synthesized. Furthermore, the Atom Transfer Radical Co-Polymerization of NVCL and NVP with non-polar monomers was investigated with the aim to obtain amphiphilic material with tunable polarity. The ATRP of vinyl acetate (VAc), which was poorly optimized, was studied trying to obtain poly(VAc) with low polydispersity (<1.25), pre-determinable molecular weight and living character. The optimization of the ATRP of VAc and the synthesis of several block copolymers, synthesized in presence of different experimental conditions, can significantly expand the field of materials and applications of poly(VAc) and poly(vinyl alcohol)-based products. Moreover, the synthesis of pH and temperature polymers was investigated with the aim to obtain products suitable for the development of drug-delivery systems which can be applied in anti-cancer applications. For this purpose Pluronic F127, which is thermosensitive, and poly(ethylene glycol)s were modified with pH poly[2-(N,N-dimethylamino)ethyl methacrylate] (PDMAEMA), poly[2-(N,N-diethylamino)ethyl methacrylate] (PDEAEMA) and poly[2-(N,N-diisopropylamino)ethyl methacrylate] (PDIAEMA). The methacrylic moieties have different pKa, and they give to the synthesized materials the desired pH responsiveness. The gelation behavior of the obtained products was investigated by rheological measurements; the dimension of the polymeric aggregates in water solutions at different pH was studied by DLS and the drug-incorporation as a function of pH was determined in systems with stable pH and in systems in which the pH was decreased progressively. All the cited investigation allowed to well-characterized the behavior and the structure of polymeric aggregates in water solution and they also allowed to determine their pH and temperature responsiveness.