New biosourced AA and AB monomers from 1,4:3,6-dianhydrohexitols, Isosorbide, Isomannide, and Isoidide

Abstract

In the present work, we propose the synthesis of a new family of sugar derived 1,4:3,6-dianhydrohexitol based AA/AB-type monomers. Unprecedented diacids based on Isomannide and Isoidide were elaborated with high yields and showed interestingly high melting point ranges (240–375 °C). Optimization of reaction conditions (temperature, time of reaction, and reactant ratios) has been investigated to synthesize the key intermediate of a set of AB monomers with acid, ester, and acid chloride functionalities. Isosorbide based ether benzoic acid AB monomer was polymerized and characterized by NMR and DSC techniques. The results show a semicrystalline behavior of the obtained polymer thanks to the controlled stereoregular arrangement of the AB starting monomer.

Microwave-assisted synthesis of isosorbide-derived diols for the preparation of thermally stable thermoplastic polyurethane

“…Indeed, the inversion of configuration of the C-5 bearing the endo -tosyl group (in compounds 3a and 3b ) reported before results in the formation of an exo (C–O) bond in compounds 4a and 4b since only an exo -linkage can bridge the C-5 of 1,4:3,6-Dianhydrohexitol unit with the adjacent oxygen atom. This is confirmed by the analysis of the number of signals observed in the 1 H and 13 C NMR spectra of diols 4a and 4b (see below) and by comparison with similar isoidide based compounds as reported in literature [ 7,38,39 ].…”

A rigid spirocyclic diol from fructose-based 5-hydroxymethylfurfural: synthesis, life-cycle assessment, and polymerization for renewable polyesters and poly(urethane-urea)s

“…For example, isosorbide (a bicyclic sugarbased diol) was reported to produce diversified polymer structures with increased T g . [32][33][34][35][36][37][38] Sugar-based polyols like sorbitol and mannitol have been converted into rigid monomers (e.g. diols, diamines, dicarboxylates) with bicyclic structures and used in polymerizations of polyesters, polyurethanes and polyureas.…”

Rigid diol bearing 6‐6‐6 fused ring system derived from naturally occurring myo‐inositol and its polyaddition with diisocyanates

“…Because they also have rigid bicyclic structures, the corresponding polymers exhibit excellent thermal properties. In addition, these diols, namely dianhydrohexitols and diacetals of sugars, are useful not only as monomers but also as precursors of other types of monomers, such as dicarboxylic acids, diamines, and vinyl monomers, among others …”