Titanium-catalyzed synthesis of polymyrcene and polyanethol and application as sustainable additives for poly(lactic acid)

The replacement of fossil-derived plastics with those obtained from bio-based resources, which present suitable performance to be employed as commodity plastics is currently an important field of research, given the urgent need to transition from a fossil-based to a more sustainable economy. In this context, this work is focused on the application of a catalytic system based on silsesquioxane-cyclopentadienyl titanium complexes for the preparation of bio-based polymers, which can be used as additives to improve the poor material properties of a biodegradable polymer such as poly(lactic acid) (PLA). These titanium complexes, when activated with methylaluminoxane or with triflate salts, are shown to be capable of the polymerization of two bio-based monomers: myrcene and anethole. It is notable that polymerizations with these two distinct monomers take place through different mechanisms. The resulting polymyrcene (PMy) and polyanethol (PAN) have been applied as modifiers for PLA. Binary blends of PMy and PLA exhibited a considerable decrease in Tg and the promotion of PLA crystallization for a PMy content below 15 wt%. The mechanical properties of the PLA/PMy blends also displayed plasticization, with a decrease in the elastic modulus and enhanced plasticity, which resulted in less fragile systems compared to pure PLA. Morphological analysis has indicated a partially miscible, phase-separated system with micron-sized domains. In contrast, PAN completely inhibited PLA crystallization and the PLA/PAN blends were immiscible, but well-dispersed, a phase-separated system was obtained in solvent-casting film preparation with very small PAN domains. The blends showed higher tensile modulus than pure PLA and an absence of plastic behaviour, resulting in more fragile systems upon the addition of PAN to PLA.