Isosorbide is a biobased compound which could become in the near future an advantageous competitor of petroleum-derived components in the synthesis of polymers of different nature. When the reactivity of isosorbide is not enough, it can be successfully transformed into secondary building blocks, such as isosorbide bis(methyl carbonate), which provides extra functionalities for polymerization reactions with diols or diamines. The present review summarizes the possibilities for isosorbide as a green raw material to be used in the synthesis of polycarbonates and polyurethanes to obtain products of similar or enhanced properties to the commercial equivalents. GRAPHICAL ABSTRACT

The substitution of fossil resources by alternatives derived from biomass is a reality that is taking on a growing relevance in the chemical and energy industries. In this sense, fats, oils, and their derived products have become indispensable inputs due to their broad functional attributes, stable price and sustainable character. Acrylated vegetable oils are considered to be very versatile materials for very broad applications (such as in adhesives, coatings or inks) since, in the presence of photoinitiators, they can be polymerized by means of UV-initiated free radical polymerizations. The usual process for the synthesis of acrylate vegetable oils consists in reacting epoxidized oils derivatives with acrylic acid. Here, the influence of different catalysts on the activity and selectivity of the process of acrylation of epoxidized soybean oil is studied. In addition, a novel one-step method for direct acrylation of vegetable oils is also explored. This new approach advantageously uses the original vegetable resource and eliminates intermediate reactions, thus being more environmentally efficient. This study offers a simple and low-cost option for synthesizing a biomass-derived monomer and studies the potential for the 3D printing of complex structures via digital light processing (DLP) 3D printing of the thus-obtained novel sustainable formulations.

Isosorbide bis(methyl carbonate) (IBMC) is a scarcely studied green chemical with potential applications in the manufacturing of non-isocyanate polyurethanes and bisphenol A-free polycarbonates. Its synthesis by transesterification of isosorbide with dimethyl carbonate (DMC) is very negatively influenced by the presence of small amounts of acidic impurities in isosorbide when heterogeneous inorganic carbonates such as potassium and cesium carbonates are used as catalysts. In this paper it is shown that the problem can be solved by using homogeneous catalysts consisting of nitrogenated bases and superbases having a suitable dual nucleophilic–basic character and able to form a highly reactive acyl intermediate with the electrophilic reactant DMC. Cycloaliphatic secondary and tertiary amines, guanidines and amidines covering a nucleophilicity parameter (N) range between 13.58 and 20.58 in either acetonitrile or dichloromethane, and a pK_a range in acetonitrile between 15.68 and 26.02 have been tested in batchwise mode. Highly active catalysts leading to hydroxyl conversions of 84–93% require a minimum N of 16 and a pK_a ranging from 18.0 to 26.0. Within this pK_a range, N must increase by about 0.5–0.6 units per each unit the pK_a falls to keep the catalytic activity, indicating that nucleophilicity has approximately twice as much influence as basicity on the catalytic activity. One guanidine (TBD), one amidine (DBN) and three cycloaliphatic secondary amines (N-methylpyrrolidine, quinuclidine and DABCO) have been found to be excellent catalysts at 5 mol% vs. ISO. The side reaction leading to oligomer formation is not avoided, with oligomers, mainly the dimer, affording 6 wt% of the crude product independently of hydroxyl-conversion and catalyst type.

The acrylation degree of vegetable oils plays a relevant role in determining the mechanical properties of the resulting polymers. Both epoxide and acrylate functionalities participate in polymerization reactions, producing various types of chemical bonds in the polymer network, which contribute to specific properties such as molecular size distribution, crosslinking degree, and glass transition temperature (Tg). The accurate identification of epoxide and acrylated groups in triglyceride molecules helps to predict their behavior during the polymerization process. A methodology based on analytical spectrometric techniques, such as direct infusion, mass spectrometry with electrospray ionization, and ultra-high-performance liquid chromatography, is used in combination with FTIR and ¹H NMR to characterize the epoxy and acrylic functionalities in the fatty chains with different numbers of carbon atoms of partially acrylated triglycerides obtained by a non-catalytic reaction.