Nowadays the use of vegetable oils as polymer precursors is the subject of growing interest in the academic and industrial communities. Many synthetic pathways can be pursued from natural vegetable oils to yield different functionalized derivatives – also called synthons – and polymers, such as polyesters, polyurethanes, polyamides, etc. Herein, we widely overview recent progress in the preparation of vegetable oil-based thermoplastic polymers and, more precisely, thermoplastic polyesters and polyurethanes. Extra focus is also placed on the synthesis sustainability of these polymeric materials via atom efficient techniques, “green” catalyses and processes. The achievable bio-sourced polymers cover a wide range of thermo-mechanical properties that can respond to most of the current applications of synthetic polymers.

As we passed the 20th anniversary of the publication of the twelve principles of green chemistry, the sustainable modification of cellulose, being the most abundant bio-based polymer, is certainly worth considering. Many researchers work on an efficient valorization of this renewable resource due to its manifold and promising application possibilities, but very often the use of non-sustainable approaches (i.e. solvents, reactants and modification approaches) only addresses the renewability aspect of cellulose, while neglecting most or all of the other principles of green chemistry. In this review, we have employed the use of E-factors together with basic toxicity information to compare between various approaches for homogeneous cellulose modification. This approach, though simple and certainly not overarching, can provide a quick and useful first sustainability assessment. Therefore, in order to achieve a truly sustainable modification of cellulose, its renewability combined with mild and efficient reaction protocols is crucial in order to obtain sustainable materials that are capable of reducing the overall negative impact of today’s fossil-based polymeric materials.

Novel linear polyurethanes were synthesized by bulk polyaddition of diamines with two vegetable-based biscarbonates produced from oleic acid methyl ester. Internal carbonated fatty acid diester (ICFAD) and terminal carbonated fatty acid diester (TCFAD) were obtained by the reaction of their epoxide precursors with CO₂. Terminal epoxy fatty acid diester (TEFAD) was found to be more soluble and more reactive in CO₂ than internal epoxy fatty acid diester (IEFAD). Polyurethanes obtained by polyaddition of TCFAD and ICFAD with diamines exhibit molecular weights up to 13 500 g mol⁻¹ and glass transitions around −15 °C. Amide linkages were not observed when secondary diamine was used as the comonomer.