Abstract :
[en] Methylene heterocyclic compounds (MHCs) are an attractive monomer class for radical polymerization allowing the introduction of heteroatoms and functionalities in the side groups or in the main chain of polymers. The vast majority of the MHCs considered in polymer synthesis, however, are conjugated derivatives, so well adapted to the modification of macromolecules derived from conjugated monomers but not suited to copolymerize with some industrially important non-conjugated less activated monomers (LAMs) such as vinyl acetate (VAc), vinyl amides, ethylene, etc. Moreover, most of them are petroleum-based compounds and the development of biomass-derived MHCs still need to be addressed. The present thesis, carried out in the frame of the BioFact-EOS program dedicated to the development of bio-based chemicals and polymers, addresses the above mentioned limitations by developing non- conjugated MHCs, including CO2-derived compounds, able to copolymerize with LAMs and to produce a new range of functional copolymers. In particular, we developed the synthesis of ?-methylene-?-butyrolactone (?M?BL) and of the CO2-sourced 4,4-dimethyl-5- methyleneoxazolidin-2-one (DMOx), and explored their potential as building blocks for the preparation of functional copolymers. Their reversible deactivation radical copolymerization with VAc, N-vinyl caprolactam (NVCL) and ethylene, was notably studied leading to a series of ?M?BL or DMOx containing copolymers with controlled molar mass and compositions. Various post-polymerization modifications of these MHC-based copolymers gave access to unique stimuli responsive materials including pH-sensitive acid-functional poly(vinyl alcohol), dual pH/thermo-responsive acid-bearing PNVCL, pH/thermo/metal ion-responsive amino alcohol-functional poly(vinyl alcohol) as well as unprecedented pH-responsive amino- functional ethylene/vinyl alcohol copolymers. Overall, this work broadens the scope of the radical polymerization of MHCs which will further develop and become a powerful tool in the hands of polymer chemists.