From the Synthesis of Biobased Cyclic Carbonate to Polyhydroxyurethanes: A Promising Route towards Renewable Non-Isocyanate Polyurethanes.

With a global production of around 18 million tons (6th among all polymers) and a wide range of applications, such as rigid and soft foams, elastomers, coatings, and adhesives, polyurethanes (PUs) are a major polymer family. Nevertheless, they present important environmental and health issues. Recently, new and safer PUs, called non-isocyanate polyurethanes (NIPUs), have become a promising alternative to replace conventional PUs. Sustainable routes towards NIPUs are discussed herein from the perspective of green chemistry. The main focus is on the reaction between biobased carbonates and amines, which offers an interesting pathway to renewable polyhydroxyurethanes (PHUs). An overview of different routes for the synthesis of PHUs draws attention to the green synthesis of cyclic carbonate (CC) compounds and the aminolysis reaction. Current state-of-the-art of different biobased building blocks for the synthesis of PHUs focuses on CC compounds. Three classes of compounds are defined according to the feedstock: 1) vegetable fats and oils, 2) starch and sugar resources, and 3) wood derivatives. Finally, biobased PHU properties are discussed.

Cardanol and Eugenol Based Flame Retardant Epoxy Monomers for Thermostable Networks.

Epoxy materials have attracted attention for many applications that require fireproof performance; however, the utilization of hazardous reagents brings about potential damage to human health. Eugenol and cardanol are renewable, harmless resources (according to ECHA) that allow the achievement of synthesis of novel phosphorylated epoxy monomers to be used as reactive flame retardants. These epoxy building blocks are characterized by 1H NMR and 31P NMR (nuclear magnetic resonance) and reacted with a benzylic diamine to give bio-based flame-retardant thermosets. Compared to DGEBA (Bisphenol A Diglycidyl Ether)-based material, these biobased thermosets differ by their cross-linking ratio, the nature of the phosphorylated function and the presence of an aliphatic chain. Eugenol has led to thermosets with higher glass transition temperatures due to a higher aromatic density. The flame-retardant properties were tested by thermogravimetric analyses (TGA), a pyrolysis combustion flow calorimeter (PCFC) and a cone calorimeter. These analyses demonstrated the efficiency of phosphorus by reducing significantly the peak heat release rate (pHRR), the total heat release (THR) and the effective heat of combustion (EHC). Moreover, the cone calorimeter test exhibited an intumescent phenomenon with the residues of phosphorylated eugenol thermosets. Lastly, the higher flame inhibition potential was highlighted for the phosphonate thermoset.