Design, synthesis, and properties of novel bio-based and ethylene-based copolymers

Renewable monomers have the potential to replace petroleum-derived monomers for reversible deactivation radical polymerisations (RDRP) for a variety of applications, such as adhesives and coatings. Yet, challenges in the polymerisation of non-activated and often internal double bonds found in natural molecules still remain. Moreover, functionalisation pathways attaching renewably-sourced double bonds to natural molecules are rare and sustainable strategies using catalytic or enzymatic reactions are sought after.
This thesis aims to introduce a set of renewable monomers for reversible deactivation radical polymerisation (RDRP), namely organometallic-mediated radical polymerisation (OMRP) using a cobalt complex, in the quest for renewable and functional (co)polymers. This particular type of OMRP was chosen because it controls the polymerisation of a large range of non-activated monomers with excellent control over the chain growth process under mild experimental conditions. The monomers prepared in this thesis were obtained from plant oils and/or CO2 via catalytic reactions and contain ester and carbonate functionalities of interest for post-polymerisation modifications. Successful copolymerisations with monomers bearing non-activated double bonds, namely vinyl acetate and ethylene, were performed using OMRP under mild conditions and the comonomer content was tuned via the initial polymerisation feed or the ethylene working pressure. The introduction of carbonate moieties into vinyl acetate copolymers allowed for the synthesis of three discrete functional poly(vinyl alcohol) copolymers. Moreover, the ability to incorporate such carbonate functionalities into polyethylene copolymers by OMRP was shown for the first time. Highly linear ethylene copolymers over a broad range of carbonate content were obtained with significantly altered properties compared to homo-polyethylene. Particularly the ability to finely tune the molecular copolymer parameters, such as molecular weight and copolymer architecture, allows a systematic study of their influence on the compatibilisation capability of such copolymers. The potential of polyethylene copolymers bearing functional groups as compatibilisers was highlighted for poly(ethylene-co-vinyl acetate) copolymers. Finally, a fully renewable compatibiliser, based on starch and high oleic sunflower oil, obtained by non-radical means was applied to cellulose/LDPE composites. An improved cellulose dispersion within the matrix was observed by rheology, while the mechanical properties, notably Young’s modulus, was increased.
This work aims to highlight the unexplored potential of renewable resources for the synthesis of functional polymers for their application in polyolefin composites.