Environmental concerns continuously drive research to find alternatives to fossil-based constituents in a greener way. Industrial polyurethane (PU) foams are usually obtained from the polyaddition reaction between fossil-based polyols and polymeric 4,4′-methylene bis(phenyl isocyanate). The very recent development at the industrial scale of microalgae production provides accessibility to original building blocks and new macromolecular architectures. In this study, the green chemistry principles were highly prioritized to synthesize different polyols from microalgae oil. The resulting microalgae-derived polyols were structurally, chemically, and physically characterized and then compared. PU foams were synthesized using a conventional fossilbased polyol substituted incrementally by microalgae-derived polyols. The corresponding cellular materials were extensively characterized in terms of reactivity, morphology, and performances and then compared to conventional foams. A new biobased foam formulation containing 25 wt % biobased polyols matched the compliance levels of a fossil-based reference foam. For the first time, a catalyst-free foam with a similar density as the reference was achieved with a biobased triglyceride catalytic polyol.

Nowadays, polyols are basic chemicals for the synthesis of a large range of polymers, such as polyurethane foams (PUF), which are produced with several other compounds, such as polyisocyanates. During the last decades, the oleo-chemistry has developed several routes from glycerides to polyols for the polyurethanes (PU) industry to replace mainly conventional fossil-based polyols. A large range of biobased polyols can be now obtained by epoxidation of the double bonds and ring-opening (RO) of the subsequent epoxides with different chemical moieties. In preliminary studies, the RO kinetics of an epoxidized model molecule (methyl oleate) with ethanol and acetic acid were investigated. Subsequently, polyols that were derived from unsaturated triglycerides were explored in the frame of e.g., PUF formulations. Different associations were studied with different mono-alcohols derived from epoxidized and ring-opened methyl oleate while using several ring-openers to model such systems and for comparison purposes. Kinetic studies were realized with the pseudo-first-order principle, meaning that hydroxyls are in large excess when compared to the isocyanate groups. The rate of isocyanate consumption was found to be dependent on the moiety located in β-position of the reactive hydroxyl, following this specific order: tertiary amine >> ether > ester. The tertiary amine in β-position of the hydroxyl tremendously increases the reactivity toward isocyanate. Consequently, a biobased reactive polyurethane catalyst was synthesized from unsaturated glycerides. These approaches offer new insights regarding the replacement of current catalysts often harmful, pungent, and volatile used in PU and PUF industry, in order to revisit this chemistry.