The epoxidized group, also known as the oxirane group, can be considered as one of the most crucial rings in chemistry. Due to the high ring strain and the polarization of the C–O bond in this three-membered ring, several reactions can be carried out. One can see such a functional group as a crucial intermediate in fuels, polymers, materials, fine chemistry, etc. Literature covering the topic of epoxidation, including the catalytic aspect, is vast. No review articles have been written on the catalytic synthesis of short size, intermediate and macro-molecules to the best of our knowledge. To fill this gap, this manuscript reviews the main catalytic findings for the production of ethylene and propylene oxides, epichlorohydrin and epoxidized vegetable oil. We have selected these three epoxidized molecules because they are the most studied and produced. The following catalytic systems will be considered: homogeneous, heterogeneous and enzymatic catalysis.

Polyurethane (PU) foams represent a wide class of polymeric materials, having applications in different sectors ranging from automotive, packaging, and cushioning/bedding to construction. However, their synthesis requires the use of petrol-based components, which are mostly harmful and toxic isocyanates. Considering this, non-isocyanate polyurethane (NIPU) foams have been demonstrated to be promising alternatives to conventional PUs, which are obtained through “isocyanate-free” routes such as the aminolysis of cyclic carbonates with diamines. The building blocks of NIPU foams can be derived from different bio-sources, such as vegetable oils, sugars, and terpenes. Moreover, the final NIPU materials can be fully reprocessed and recycled owing to the presence of suitable functional groups that facilitate dynamic bond exchange. This review aims to comprehensively describe the current state-of-the-art concerning the synthesis and applications of NIPU and hybrid NIPU foams and is divided into three sections: (i) an outline of the synthesis of bio-based NIPU precursors, i.e. cyclic and linear carbonates, diamines and carbamates, from biomass-derived and waste sources such as vegetable oils and CO₂ and via environmentally friendly approaches; (ii) analysis of the reprocessability and recyclability of NIPU and composite NIPU foams; and (iii) evaluation of the environmental impacts of NIPU precursors and foams using the life cycle assessment (LCA) technique, preliminary investigations of their techno-economic analysis (TEA), and description of future perspectives.

Pelargonic acid (PA) is commercially obtained by oxidative cleavage of fatty acid double bonds. Its esters are interesting compounds used to create bio-based products. An industrially relevant application of these compounds is in the field of solvent manufacturing and formulation of green lubricating oils. The physical-chemical and rheological properties of these esters are influenced by the structural features of the alcohol used as starting materials, such as chain length, number of unsaturation, and degree of branching. This work provides an in-depth study of the existing structure-properties relations for fatty acid alkyl esters obtained from PA and different alcohols [i.e., 2-ethylhexanol (EtHex), ethylene glycol, 1,3-propanediol, 1,4-butanediol, trimethylolpropane, and pentaerythritol]. The aim is to evaluate the use of the synthesized product for the formulation of bio-based lubricants. The chosen alcohols are frequently employed in the preparation of bio-based lubricants. In addition, most of them, such as EtHex and diols, can be derived from biomass sources, contributing to the sustainability of the obtained products. For comparison purposes, some of these alcohols were also used for the synthesis of the corresponding oleic acid esters, which were chosen as a benchmark due to their common use in the synthesis of bio-based lubricants. The influence of the structural factors on the viscosity, pour point (PP), and oxidation stability of the synthesized esters was highlighted by comparing the obtained results. Pelargonates showed lower viscosities and higher PPs than that of the oleates, but they present high stabilities to the oxidation due to the absence of unsaturation.

In the last few years, the depletion of the fossil sources and their negative effect on the environment has led to find new alternatives; among these, biodiesel is considered one of the most promising for this purpose. Biodiesel can be produced from the transesterification of vegetable oils or animal fats, obtaining glycerol as a by-product. Glycerol can be used in different processes and one of the most interesting is the condensation with acetone to produce solketal. Among its applications, plasticizers, solvents, and pharmaceutical formulations are the most common. In this work, the attention was focused on the reaction between glycerol and acetone to give solketal promoted by an iron(III) complex. The reaction mechanism was hypothesized, and the kinetics was studied in a batch reactor. Finally, the thermodynamic and kinetic parameters were determined with a reliable model investigating the phenomena that occurred in the reaction network.

The activity of MOF-5-based solids has been exploited in the simultaneous transesterification and esterification of acid vegetable oils. For this purpose, three different types of MOF-5 have been synthesized and characterized, and then tested in the above-mentioned reactions. It has been demonstrated that the “regular MOF-5” was a suitable catalyst for biodiesel synthesis from waste oil also, rich in FFA (Free Fatty Acids). Moreover, to identify the true structure that acts in the reactions and possible structural modifications due to the presence of alcohols, proper studies have been performed. The results have evidenced a distortion of the regular structure of MOF-5 due to the breakage of some zinc bonds between the cluster and organic framework.